Heterocyclic amide compound

ABSTRACT

The present invention provides a heterocyclic amide compound of Formula (1), and an agricultural chemical containing it, particularly a herbicide: 
     
       
         
         
             
             
         
       
     
     in which Q is an aromatic heterocycle of any one of Q-1 to Q-5, W is an aromatic heterocycle of W-1, W-2, or W-3, X is an oxygen atom, etc., R 1a  is a hydrogen atom, a halogen atom, or C 1-6  alkyl, etc., R 1b  is a hydrogen atom, R 1c  is C 1-6  alkyl, R 2a  is a halogen atom, or C 1-6  alkyl, etc., R 2c  is C 1-6  haloalkyl, R 3  is a hydrogen atom, etc., R 4a , R 4b , R 4c  and R 4d  are each independently a hydrogen atom, or C 1-6  alkyl, etc., R 5a , R 5b  and R 5c  are each independently a hydrogen atom, or C 1-6  alkyl, etc., and n is an integer of 0, 1, 2 or 3.

TECHNICAL FIELD

The present invention relates to a novel heterocyclic amide compound and a salt thereof, and agricultural chemicals, in particular herbicides, containing the heterocyclic amide compound and the salt thereof as an active component. The agricultural chemical in the present invention means an insecticide/acaricide, a nematicide, a herbicide, a bactericide and the like in agricultural and horticultural fields.

BACKGROUND ART

For example, a certain type of heterocyclic amide compounds has been disclosed in Patent Documents 1 to 6. The heterocyclic amide compound according to the present invention, however, has not been disclosed at all.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: International Publication No. 2012/028579 (WO 2012/028579)

Patent Document 2: International Publication No. 2012/123409 (WO 2012/123409)

Patent Document 3: International Publication No. 2012/123416 (WO 2012/123416)

Patent Document 4: International Publication No. 2012/126932 (WO 2012/126932)

Patent Document 5: International Publication No. 2013/017559 (WO 2013/017559)

Patent Document 6: International Publication No. 2013/064457 (WO 2013/064457)

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

An object of the present invention is to provide a chemical substance that reliably exerts effects on various weeds in a low application amount of the chemical substance, has reduced land pollution and influence on succeeding crops and has a high level of safety, and is useful as an active component of herbicides.

Means for Solving the Problem

As a result of intensive investigation for solving the problem, the inventors of the present invention have found that a novel heterocyclic amide compound of Formula (1) according to the present invention has excellent herbicidal activity as a herbicide and a high level of safety to target crops as well as almost no adverse effect on non-target creatures such as mammals, fish, and beneficial insects, and that the compound is an extremely useful compound, and thus the inventors have accomplished the present invention.

More specifically, the present invention relates to the following [1] to [115].

[1]

A heterocyclic amide compound of Formula (1):

[where Q is an aromatic heterocycle of any one of Q-1 to Q-5;

W is an aromatic heterocycle of W-1, W-2, or W-3;

X is an oxygen atom or a sulfur atom;

R^(1a) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₃₋₆ cycloalkenyl, —C(O)R⁸, —C(O)OR¹⁶, cyano, —OR⁹, —S(O)_(m1)R¹⁰, —N(R¹¹)R¹², —C(═NR^(12b))R^(8b), phenyl, phenyl substituted with (R⁷)_(p), naphthyl, or any one group of U-1 to U-25;

R^(1b) is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, phenyl, phenyl substituted with (R⁷)_(p), naphthyl, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a));

R^(1c) is C₁₋₆ alkyl;

R^(2a) is a halogen atom, C₁₋₆ alkyl, C₁₋₆ haloalkyl, —C(O)R¹⁸, —C(O)OR²⁴, cyano, nitro, —OR¹⁹, —S(O)_(m3)R²⁰, —N(R²¹)R²², phenyl, or phenyl substituted with (R⁷)_(p); when n is an integer of 2 or more, R^(2a) are optionally the same as or different from each other, and when two R^(2a) are adjacent, the two adjacent R^(2a) optionally form a 6-membered ring together with carbon atoms bonded to each R^(2a) by forming —CH═CH—CH═CH—;

R^(2c) is C₁₋₆ haloalkyl;

R³ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, —C(O)R²⁵, or —C(O)OR²⁶;

R^(4a) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R²⁷, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, —NH₂, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, —NHC(O)R⁸, phenyl, phenyl substituted with (R²⁸)_(r), 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a));

R^(4b) is a hydrogen atom, a halogen atom, cyano, nitro, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R²⁷, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, —C(O)OR¹⁶, —OR³⁸, —S(O)_(m3)R²⁰, —NH₂, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, —NHC(O)R⁸, phenyl, phenyl substituted with (R²⁸)_(r), 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a));

R^(4c) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R²⁷, phenyl, phenyl substituted with (R²⁸)_(r), 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a));

R^(5d) is a hydrogen atom, C₁₋₆ alkyl, or (C₁₋₆) alkyl optionally substituted with R³⁵;

U-1 to U-6, U-6a, U-7 to U-10, U-10a, U-11, U-11a, U-12, U-12a, U-13, U-13a, U-14 to U-22, U-22a, U-23, U-24, U-25, and U-26 are respective heterocycles of the following structures;

R^(5a) and R^(5b) are each independently a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, phenyl, or phenyl substituted with (R²⁸)_(r);

R^(5c) is a hydrogen atom, C₁₋₆ alkyl, or (C₁₋₆) alkyl optionally substituted with R³⁶, or R^(5c) optionally forms a 6-membered ring together with a nitrogen atom to which R^(5c) is bonded and a carbon atom to which R^(4d) is bonded by forming —(CH₂)₄— or —CH═CH—CH═CH— with R^(4d);

R⁶ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, —OR¹³, —S(O)_(m2)R¹⁴, phenyl, or phenyl substituted with (R⁷)_(p);

R⁷ is a halogen atom, cyano, nitro, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, C₁₋₆ alkylcarbonyl, C₃₋₆ cycloalkylcarbonyl, C₁₋₆ haloalkylcarbonyl, C₃₋₆ halocycloalkylcarbonyl, C₁₋₆ alkoxycarbonyl, C₁₋₆ halo alkoxycarbonyl, C₁₋₆ alkylaminocarbonyl, C₁₋₆ haloalkylaminocarbonyl, di(C₁₋₆ alkylamino)carbonyl, —OR¹⁵, —S(O)_(m3)R²⁰, C₁₋₆ alkylaminosulfonyl, di(C₁₋₆ alkyl)aminosulfonyl, —NH₂, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a));

R⁸ is a hydrogen atom, C₁₋₆ alkyl, or —N(R^(11a))R^(12a);

R^(8b) is a hydrogen atom or C₁₋₆ alkyl;

R⁹ is a hydrogen atom, C₁₋₆ alkyl, or phenyl;

R¹⁰ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, or C₂₋₆ haloalkynyl;

R¹¹ and R¹² are each independently a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, phenylsulfonyl, phenyl, phenyl substituted with (R⁷)_(p), U-7, U-8, U-9, or U-14 to U-19, or R¹¹ optionally forms a 3-7-membered ring together with a nitrogen atom to which R¹¹ and R¹² are bonded by forming a C₂₋₆ alkylene chain together with R¹², and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)₂, or N(R³³) and is optionally substituted with an oxo group or a thioxo group;

R^(11a) and R^(12a) are each independently a hydrogen atom, C₁₋₆ alkyl, or phenyl, or R^(11a) optionally forms a 3-7-membered ring together with a nitrogen atom to which R^(11a) and R^(12a) are bonded by forming a C₂₋₆ alkylene chain together with R^(12a), and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)₂, or N(R³³) and is optionally substituted with an oxo group or a thioxo group;

R^(12b) is —OR^(19b);

R¹³ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, —C(O)R⁸, or phenyl;

R¹⁴ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, or phenyl;

R¹⁵ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, or C₃₋₆ cycloalkenyl;

R¹⁶ is a hydrogen atom, C₁₋₆ alkyl, or (C₁₋₆) alkyl optionally substituted with R³⁷;

R¹⁸ is a hydrogen atom or C₁₋₆ alkyl;

R¹⁹ is a hydrogen atom, C₁₋₆ alkyl, or phenyl;

R^(19b) is a hydrogen atom or C₁₋₆ alkyl;

R²⁰ is C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, or C₃₋₆ cycloalkenyl;

R²¹ and R²² are each independently a hydrogen atom, C₁₋₆ alkyl, or phenyl, or R²¹ optionally forms a 3-7-membered ring together with a nitrogen atom to which R²¹ and R²² are bonded by forming a C₂₋₆ alkylene chain together with R²², and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)₂, or N(R³⁹) and is optionally substituted with an oxo group or a thioxo group;

R²⁴ is a hydrogen atom or C₁₋₆ alkyl;

R²⁵ and R²⁶ are each independently a hydrogen atom, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, or phenyl;

R²⁷ is a halogen atom, cyano, nitro, phenyl, phenyl substituted with (R²⁸)_(r), —C(O)OR¹⁶, —OR²⁹, —S(O)_(m4)R³⁰, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a));

R²⁸ is a halogen atom, cyano, nitro, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, (C₁₋₆ alkoxy) C₁₋₆ alkyl, —OR³¹, or —S(O)_(m4)R³⁰; when t2, t3, t4, t5, t7, t8, or t9 is an integer of 2 or more, R²⁸ are optionally the same as or different from each other; further when two R²⁸ are adjacent, the two adjacent R²⁸ optionally form a 6-membered ring together with carbon atoms to which each R²⁸ is bonded by forming —CH═CH—CH═CH—;

R^(28a) is C₁₋₆ alkyl, C₁₋₆ haloalkyl, (C₁₋₆ alkoxy) C₁₋₆ alkyl, or (C₁₋₆ alkylthio) C₁₋₆ alkyl;

R²⁹, R³⁰, and R³¹ are each independently a hydrogen atom, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, or phenyl;

R³³ is a hydrogen atom or C₁₋₆ alkyl;

R³⁴ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, —OR³³, —S(O)_(m6)R³³, phenyl, phenyl substituted with (R⁷)_(p), U-1, U-3, U-7, U-8, U-9, or U-14 to U-25;

R³⁵ is a halogen atom or C₁₋₆ alkoxy;

R³⁶ is a halogen atom or C₁₋₆ alkoxy;

R³⁷ is C₁₋₆ alkoxy,

R³⁸ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, or phenyl;

R³⁹ is a hydrogen atom or C₁₋₆ alkyl;

t1 is an integer of 0 or 1;

m1, m2, m3, m4, m6, and t2 are each independently an integer of 0, 1, or 2;

n and t3 are each independently an integer of 0, 1, 2, or 3;

p and r are each independently an integer of 1, 2, 3, 4, or 5;

t4 is an integer of 0, 1, 2, 3, or 4;

t5 is an integer of 0, 1, 2, 3, 4, or 5;

t7 is an integer of 0, 1, 2, 3, 4, 5, 6, or 7;

t8 is an integer of 0, 1, 2, 3, 4, 5, 6, 7, or 8; and

t9 is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9] or a salt thereof.

[2]

The heterocyclic amide compound or the salt thereof according to [1], in which W is an aromatic heterocycle of W-1 or W-2; and

R^(2a) is a halogen atom, C₁₋₆ alkyl, C₁₋₆ haloalkyl, —C(O)R¹⁸, —C(O)OR²⁴, cyano, nitro, —OR¹⁹, or —S(O)_(m3)R²⁰, and when n is an integer of 2 or more, R^(2a) are optionally the same as or different from each other.

[3]

The heterocyclic amide compound or the salt thereof according to [2], in which R^(1b) is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, phenyl, phenyl substituted with (R⁷)_(p), naphthyl, or any one group of U-1 to U-25;

R^(4a) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R²⁷, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, —NH₂, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, —NHC(O)R⁸, phenyl, phenyl substituted with (R²⁸)_(r), or any one group of U-1 to U-26;

R⁷ is a halogen atom, cyano, nitro, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, C₁₋₆ alkylcarbonyl, C₃₋₆ cycloalkylcarbonyl, C₁₋₆ haloalkylcarbonyl, C₃₋₆ halocycloalkylcarbonyl, C₁₋₆ alkoxycarbonyl, C₁₋₆ halo alkoxycarbonyl, C₁₋₆ alkylaminocarbonyl, C₁₋₆ haloalkylaminocarbonyl, di(C₁₋₆ alkyl amino)carbonyl, —OR¹⁵, —S(O)_(m3)R²⁰, C₁₋₆ alkylaminosulfonyl, di(C₁₋₆ alkyl)aminosulfonyl, —NH₂, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, or any one group of U-1 to U-26; and

R²⁷ is a halogen atom, cyano, nitro, phenyl, phenyl substituted with (R²⁸)_(r), —C(O)OR¹⁶, —OR²⁹, —S(O)_(m4)R³⁰, or any one group of U-1 to U-26.

[4]

The heterocyclic amide compound or the salt thereof according to [3], in which R^(1a) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₃₋₆ cycloalkenyl, —C(O)R⁸, —OR⁹, —S(O)_(m1)R¹⁰, —N(R¹¹)R¹², —C(═NR^(12b))R^(8b), phenyl, phenyl substituted with (R⁷)_(p), U-3, U-5a, U-6a, U-7, U-8, U-10a, U-11a, U-12a, or U-13a;

R^(1b) is C₁₋₆ alkyl or (C₁₋₆) alkyl optionally substituted with R⁶;

R^(2a) is a halogen atom, C₁₋₆ alkyl, C₁₋₆ haloalkyl, or —S(O)_(m3)R²⁰, and when n is an integer of 2 or more, R^(2a) are optionally the same as or different from each other;

R³ is a hydrogen atom or C₁₋₆ alkyl;

R^(4a) is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, phenyl, phenyl substituted with (R²⁸), or a heterocycle of U-1, U-2, U-7, U-10a, or U-26;

R^(4b) is C₁₋₆ alkyl;

R^(4c) is a hydrogen atom;

R^(4d) is C₁₋₆ alkyl;

R^(5a) is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R₂₇, C₂₋₆ alkenyl, or phenyl;

R^(5b) is a hydrogen atom or C₁₋₆ alkyl;

R^(5c) is C₁₋₆ alkyl, or R^(5c) optionally forms a 6-membered ring together with a nitrogen atom to which R^(5c) is bonded and a carbon atom to which R^(4d) is bonded by forming —(CH₂)₄— or —CH═CH—CH═CH— with R^(4d);

R⁷ is a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, or —OR¹⁵;

R^(8b) is a hydrogen atom;

R⁹ is C₁₋₆ alkyl;

R¹⁰ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, or C₂₋₆ alkynyl;

R¹¹ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, phenylsulfonyl, phenyl, phenyl substituted with (R⁷)_(p), or U-7;

R¹² is a hydrogen atom or C₁₋₆ alkyl;

R¹¹ optionally forms a 5-6-membered ring together with a nitrogen atom to which R¹¹ and R¹² are bonded by forming a C₄₋₅ alkylene chain together with R¹², and in this case, the alkylene chain optionally contains one O, S, S(O), or S(O)₂;

R¹¹ is C₁₋₆ alkyl;

R^(12a) is a hydrogen atom;

R¹³ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, —C(O)R⁸, or phenyl;

R¹⁴ is C₁₋₆ alkyl or (C₁₋₆) alkyl optionally substituted with R³⁴;

R¹⁵ is C₁₋₆ alkyl;

R^(19b) is C₁₋₆ alkyl;

R²⁰ is C₁₋₆ alkyl;

R²⁷ is a halogen atom, phenyl, phenyl substituted with (R²⁸)_(r), —OR²⁹, —C(O)OR¹⁶, or —S(O)_(m4)R³⁰;

R²⁸ is a halogen atom, C₁₋₆ alkyl, or —OR³¹; when t2, t3, t4, t5, or t7 is an integer of 2 or more, R²⁸ are optionally the same as or different from each other; and further when two R²⁸ are adjacent, the two adjacent R²⁸ optionally form a 6-membered ring together with carbon atoms to which each R²⁸ is bonded by forming —CH═CH—CH═CH—;

R²⁹ is C₁₋₆ alkyl;

R³⁰ is C₁₋₆ alkyl;

R³¹ is C₁₋₆ alkyl;

R³³ is C₁₋₆ alkyl; and

R³⁴ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, —OR³³, —S(O)_(m6)R³³, phenyl, phenyl substituted with (R⁷)_(p), U-1, U-8, or U-22a.

[5]

The heterocyclic amide compound or the salt thereof according to [4], in which Q is an aromatic heterocycle of Q-1; and

W is an aromatic heterocycle of W-1.

[6]

The heterocyclic amide compound or the salt thereof according to [5], in which X is an oxygen atom;

R^(1a) a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₃₋₆ cycloalkenyl, —C(O)R⁸, —OR⁹, —S(O)_(m1)R¹⁰, —N(R¹¹)R¹², —C(NR^(12b))R^(8b), phenyl, phenyl substituted with (R⁷)_(p), U-5a, U-6a, U-7, U-8, U-10a, U-11a, U-12a, or U-13a;

R^(2a) is C₁₋₆ alkyl, C₁₋₆ haloalkyl, or —S(O)_(m3)R²⁰, and when n is an integer of 2 or more, R^(2a) are optionally the same as or different from each other;

R⁶ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, —OR¹³, —S(O)_(m2)R¹⁴, or phenyl substituted with (R⁷)_(p); and

R²⁷ is a halogen atom, phenyl, —OR²⁹, or —S(O)_(m4)R³⁰

[7]

The heterocyclic amide compound or the salt thereof according to [6], in which R^(4a) is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, or C₃₋₆ cycloalkyl; and

R²⁷ is a halogen atom or —OR²⁹.

[8]

The heterocyclic amide compound or the salt thereof according to [4], in which Q is an aromatic heterocycle of Q-3; and

W is an aromatic heterocycle of W-1.

[9]

The heterocyclic amide compound or the salt thereof according to [8], in which R^(1a) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, —C(O)R⁸, —S(O)_(m1)R¹⁰, —N(R¹¹)R¹², phenyl, phenyl substituted with (R⁷)_(p), U-3, U-5a, U-6a, U-8, U-10a, or U-13a;

R^(2a) is a halogen atom, C₁₋₆ alkyl, or C₁₋₆ haloalkyl, and when n is an integer of 2 or more, R^(2a) are optionally the same as or different from each other;

R⁶ is a halogen atom, —C(O)OR¹⁶, —OR¹³, —S(O)_(m2)R¹⁴, or phenyl substituted with (R⁷)_(p);

R⁷ is a halogen atom, C₁₋₆ alkyl, or —OR¹⁵;

R⁸ is a hydrogen atom or C₁₋₆ alkyl;

R¹¹ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, phenyl, or phenyl substituted with (R⁷)_(p);

R¹¹ optionally forms a 6-membered ring together with a nitrogen atom to which R¹¹ and R¹² are bonded by forming a C₅ alkylene chain together with R¹², and in this case, the alkylene chain optionally contains one O, S, S(O), or S(O)₂;

R¹⁶ is a hydrogen atom or C₁₋₆ alkyl;

R²⁷ is phenyl substituted with (R²⁸), —OR²⁹, —C(O)OR¹⁶, or —S(O)_(m4)R³⁰;

R²⁸ is a halogen atom or C₁₋₆ alkyl; and

R³⁴ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —OR³³, —S(O)_(m6)R³³, phenyl, phenyl substituted with (R⁷)_(p), U-1, or U-8.

[10]

The heterocyclic amide compound or the salt thereof according to [9], in which R^(5a) is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, or C₂₋₆ alkenyl; and

R²⁷ is —OR²⁹ or —S(O)_(m4)R³⁰.

[11]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [10], in which X is an oxygen atom.

[12]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [10], in which X is a sulfur atom.

[13]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [12], in which R³ is a hydrogen atom.

[14]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [12], in which R³ is C₁₋₆ alkyl.

[15]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [14], in which R^(2a) is C₁₋₆ haloalkyl.

[16]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [14], in which R^(2a) is a halogen atom.

[17]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [14], in which R^(2a) is —S(O)_(m3)R²⁰; and

R²⁰ is C₁₋₆ alkyl.

[18]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [14], in which R^(2a) is trifluoromethyl.

[19]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [18], in which n is an integer of 1, 2, or 3.

[20]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [18], in which n is an integer of 1.

[21]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-2; and

W is an aromatic heterocycle of W-1.

[22]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-4; and

W is an aromatic heterocycle of W-1.

[23]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-5; and

W is an aromatic heterocycle of W-1.

[24]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-1; and

W is an aromatic heterocycle of W-2.

[25]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-2; and

W is an aromatic heterocycle of W-2.

[26]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-3; and

W is an aromatic heterocycle of W-2.

[27]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-4; and

W is an aromatic heterocycle of W-2.

[28]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-5; and

W is an aromatic heterocycle of W-2.

[29]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-1; and

W is an aromatic heterocycle of W-3.

[30]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-2; and

W is an aromatic heterocycle of W-3.

[31]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-3; and

W is an aromatic heterocycle of W-3.

[32]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-4; and

W is an aromatic heterocycle of W-3.

[33]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [20], in which Q is an aromatic heterocycle of Q-5; and

W is an aromatic heterocycle of W-3.

[34]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [33], in which R^(4a) is a hydrogen atom.

[35]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [33], in which R^(4a) is a hydrogen atom or C₁₋₆ alkyl.

[36]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [33], in which R^(4a) is C₁₋₆ alkyl.

[37]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [33], in which R^(4a) is C₁₋₃ alkyl.

[38]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [33], in which R^(4a) is methyl.

[39]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [33], in which R^(4a) is ethyl.

[40]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [33], in which R^(4a) is C₃₋₆ cycloalkyl.

[41]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [33], in which R^(4a) is C₁₋₃ haloalkyl.

[42]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [41], in which R^(5a) is a hydrogen atom.

[43]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [41], in which R^(5a) is C₁₋₆ alkyl.

[44]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [41], in which R^(5a) is C₁₋₃ alkyl.

[45]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [41], in which R^(5a) is methyl.

[46]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [41], in which R^(5a) is ethyl.

[47]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [41], in which R^(5a) is (C₁₋₆) alkyl optionally substituted with R²⁷;

R²⁷ is —OR²⁹ or —S(O)_(m4)R³⁰;

R²⁹ is C₁₋₆ alkyl; and

R³⁰ is C₁₋₆ alkyl.

[48]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [41], in which R^(5a) is C₂₋₆ alkenyl.

[49]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, —CHO, —S(O)_(m1)R¹⁰, —N(R¹¹)R¹², phenyl, phenyl substituted with (R⁷)_(p), U-3, U-5a, U-6a, U-7, U-8, U-10a, U-11a, U-12a, or U-13a;

R⁶ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —C(O)OR¹⁶, —OR¹³, —S(O)_(m2)R¹⁴, phenyl, or phenyl substituted with (R⁷)_(p);

R⁸ is C₁₋₆ alkyl;

R¹⁰ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, or C₂₋₆ alkenyl;

R¹¹ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, phenyl, phenyl substituted with (R⁷)_(p), or U-7;

R¹² is a hydrogen atom or C₁₋₆ alkyl;

R¹¹ optionally forms a 5-6-membered ring together with a nitrogen atom to which R¹¹ and R¹² are bonded by forming a C₄₋₅ alkylene chain together with R¹², and in this case, the alkylene chain optionally contains one O, S, S(O), or S(O)₂;

R¹³ is a hydrogen atom, C₁₋₆ alkyl, or (C₁₋₆) alkyl optionally substituted with R³⁴;

R¹⁴ is C₁₋₆ alkyl or (C₁₋₆) alkyl optionally substituted with R³⁴;

R¹⁶ is a hydrogen atom, C₁₋₆ alkyl, or (C₁₋₆) alkyl optionally substituted with R³⁷; and

R³⁴ is cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, —OR³³, —S(O)_(m6)R³³, or U-1.

[50]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is C₁₋₆ alkyl, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, or —CHO.

[51]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is C₁₋₆ alkyl or C₃₋₆ cycloalkyl.

[52]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is C₁₋₆ alkyl.

[53]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is C₃₋₆ cycloalkyl.

[54]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶; and

R⁶ is a halogen atom.

[55]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶; and

R⁶ is cyano.

[56]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶; and

R⁶ is C₃₋₆ cycloalkyl.

[57]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶; and

R⁶ is —C(O)OR¹⁶.

[58]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is —OR¹³; and

R¹³ is C₁₋₆ alkyl.

[59]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is —OR¹³;

R¹³ is (C₁₋₆) alkyl optionally substituted with R³⁴;

R³⁴ is —OR³³; and

R³³ is C₁₋₆ alkyl.

[60]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is —S(O)_(m2)R¹⁴;

R¹⁴ is C₁₋₆ alkyl or (C₁₋₆) alkyl optionally substituted with R³⁴;

R³⁴ is a halogen atom or —OR³³; and

R³³ is C₁₋₆ alkyl.

[61]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is —S(O)_(m2)R¹⁴;

R⁸ is C₁₋₆ alkyl;

R¹⁴ is (C₁₋₆) alkyl optionally substituted with R³⁴;

R¹⁶ is C₁₋₆ alkyl;

R³⁴ is cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, —OR³³, or —S(O)_(m6)R³³; and

R³³ is C₁₋₆ alkyl.

[62]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is —S(O)_(m2)R¹⁴; and

R¹⁴ is C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, or C₂₋₆ haloalkynyl.

[63]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₃₋₆) cycloalkyl optionally substituted with R⁶; and

R⁶ is a halogen atom.

[64]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₃₋₆) cycloalkyl optionally substituted with R₆;

R⁶ is —OR¹³; and

R¹³ is C₁₋₆ alkyl.

[65]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰.

[66]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰.

R¹⁰ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, or C₂₋₆ alkenyl;

R³⁴ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, or —OR³³;

R⁸ is C₁₋₆ alkyl;

R¹⁶ is C₁₋₆ alkyl; and

R³³ is C₁₋₆ alkyl.

[67]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰; and

R¹⁰ is C₁₋₆ alkyl.

[68]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰; and

R¹⁰ is 6 cycloalkyl.

[69]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰; and

R¹⁰ is C₂₋₆ alkenyl.

[70]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰; and

R¹⁰ is C₂₋₆ alkynyl.

[71]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰;

R¹⁰ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is a halogen atom.

[72]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰;

R¹⁰ is (C₁₋₆) alkyl optionally substituted with R^(34a) and

R³⁴ is cyano.

[73]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰;

R¹⁰ is (C₁₋₆) alkyl optionally substituted with R^(34a) and

R³⁴ is C₃₋₆ cycloalkyl.

[74]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰;

R¹⁰ is (C₁₋₆) alkyl optionally substituted with R³⁴;

R³⁴ is —C(O)R⁸ and —C(O)OR¹⁶;

R⁸ is C₁₋₆ alkyl; and

R¹⁶ is C₁₋₆ alkyl.

[75]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰;

R¹⁰ is (C₁₋₆) alkyl optionally substituted with R³⁴;

R³⁴ is —OR³³; and

R³³ is C₁₋₆ alkyl.

[76]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰

R¹⁰ is (C₁₋₆) alkyl optionally substituted with R³⁴;

R³⁴ is —S(O)_(n6)R³³; and

R³³ is C₁₋₆ alkyl.

[77]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R_(1a) is —N(R¹¹)R¹².

[78]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²;

R¹¹ is C₁₋₆ alkyl;

R¹² is a hydrogen atom or C₁₋₆ alkyl.

[79]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²;

R¹¹ is (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, or C₂₋₆ alkenyl;

R¹² is a hydrogen atom or C₁₋₆ alkyl;

R³⁴ is a halogen atom, cyano, or —S(O)_(m6)R³³; and

R³³ is C₁₋₆ alkyl.

[80]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²;

R¹¹ is (C₁₋₆) alkyl optionally substituted with R³⁴;

R¹² is a hydrogen atom or C₁₋₆ alkyl;

R³⁴ is —OR³³; and

R³³ is C₁₋₆ alkyl.

[81]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²; and

R¹¹ optionally forms a 5-6-membered ring together with a nitrogen atom to which R¹¹ and R¹² are bonded by forming a C₄₋₅ alkylene chain together with R¹², and in this case, the alkylene chain optionally contains one O, S, S(O), or S(O)₂.

[82]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is a substituent of the following structure formulae:

[83]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is a substituent of the following structure formulae:

[84]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is phenyl or phenyl substituted with (R⁷)_(p).

[85]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶; and

R⁶ is phenyl or phenyl substituted with (R⁷)_(p).

[86]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is —OR¹³;

R¹³ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is phenyl or phenyl substituted with (R⁷)_(p).

[87]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is —S(O)_(m2)R¹⁴;

R¹⁴ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is phenyl or phenyl substituted with (R⁷)_(p).

[88]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰;

R¹⁰ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is phenyl or phenyl substituted with (R⁷)_(p).

[89]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²;

R¹¹ is (C₁₋₆) alkyl optionally substituted with R³⁴;

R¹² is a hydrogen atom or C₁₋₆ alkyl;

R³⁴ is phenyl or phenyl substituted with (R⁷)_(p).

[90]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²;

R¹¹ is phenyl or phenyl substituted with (R⁷)_(p); and

R¹² is a hydrogen atom or C₁₋₆ alkyl.

[91]

The heterocyclic amide compound or the salt thereof according to any one of [84] to [90], in which R⁷ is a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷ or —OR¹⁵;

R¹⁵ is C₁₋₆ alkyl;

R²⁷ is a halogen atom, —OR²⁹, or —S(O)_(m4)R³⁰; and

R²⁹ and R³⁰ are each independently C₁₋₆ alkyl.

[92]

The heterocyclic amide compound or the salt thereof according to any one of [84] to [90], in which R⁷ is a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, or —OR¹⁵;

R¹⁵ is C₁₋₆ alkyl; and

R²⁷ is a halogen atom.

[93]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is any one of heterocycles of U-1 to U-25.

[94]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is U-3, U-5a, U-6a, U-7, U-8, U-10a, U-11a, U-12a, or U-13a.

[95]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²; and

R¹¹ is U-7, U-8, U-9, or U-14 to U-19; and

R¹² is a hydrogen atom or C₁₋₆ alkyl.

[96]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²;

R¹¹ is U-7; and

R¹² is a hydrogen atom or C₁₋₆ alkyl.

[97]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰;

R¹⁰ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is U-7, U-8, U-9, or U-14 to U-19.

[98]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰;

R¹⁰ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is U-1, U-3, or U-20 to U-25.

[99]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —S(O)_(m1)R¹⁰;

R¹⁰ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is U-1, U-3, or U-22a.

[100]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²;

R¹¹ is (C₁₋₆) alkyl optionally substituted with R³⁴;

R¹² is a hydrogen atom or C₁₋₆ alkyl; and

R³⁴ is U-7, U-8, U-9, or U-14 to U-19.

[101]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²;

R¹¹ is (C₁₋₆) alkyl optionally substituted with R³⁴;

R¹² is a hydrogen atom or C₁₋₆ alkyl; and

R³⁴ is U-1, U-3, or U-20 to U-25.

[102]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is —N(R¹¹)R¹²;

R¹¹ is (C₁₋₆) alkyl optionally substituted with R³⁴;

R¹² is a hydrogen atom or C₁₋₆ alkyl; and

R³⁴ is U-1, U-3, or U-22a.

[103]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is ⁻OR¹³;

R¹³ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is U-7, U-8, U-9, or U-14 to U-19.

[104]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is ⁻OR¹³;

R¹³ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is U-1, U-3, or U-20 to U-25.

[105]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is ⁻OR¹³;

R¹³ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is U-1, U-3, or U-22a.

[106]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is ⁻S(O)_(m2)R¹⁴;

R¹⁴ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is U-7, U-8, U-9, or U-14 to U-19.

[107]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is ⁻S(O)_(m2)R¹⁴;

R¹⁴ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is U-1, U-3, or U-20 to U-25.

[108]

The heterocyclic amide compound or the salt thereof according to any one of [1] to [48], in which R^(1a) is (C₁₋₆) alkyl optionally substituted with R⁶;

R⁶ is ⁻S(O)_(m2)R¹⁴;

R¹⁴ is (C₁₋₆) alkyl optionally substituted with R³⁴; and

R³⁴ is U-1, U-3, or U-22a.

[109]

The heterocyclic amide compound or the salt thereof according to any one of [93] to [108], in which t1, t2, t3, t4, t5, t7, t8, and t9 are each independently an integer of 0.

[110]

The heterocyclic amide compound or the salt thereof according to any one of [93] to [108], in which R²⁸ is a halogen atom, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl, (C₁₋₆ alkoxy) C₁₋₆ alkyl, —OR³¹, or —S(O)_(m4)R³⁰.

[111]

The heterocyclic amide compound or the salt thereof according to any one of [93] to [108], in which R²⁸ is a halogen atom.

[112]

The heterocyclic amide compound or the salt thereof according to any one of [93] to [108], in which R²⁸ is C₁₋₆ alkyl.

[113]

The heterocyclic amide compound or the salt thereof according to any one of [93] to [108], in which R²⁸ is C₁₋₆ alkoxy.

[114]

An agricultural chemical comprising one or two or more of compounds selected from the heterocyclic amide compound and the salt thereof as described in any one of [1] to [113] as an active component.

[115]

A herbicide comprising one or two or more of compounds selected from the heterocyclic amide compound and the salt thereof as described in any one of [1] to [113] as an active component.

Effects of the Invention

The compound of the present invention has excellent herbicidal activity to various weeds and has a high level of safety to the target crops. In addition, the compound of the present invention has almost no adverse effect on non-target creatures such as mammals, fish, and beneficial insects and has light environmental burden due to low residual properties.

Accordingly, the present invention can provide a useful herbicide in the agricultural and horticultural fields such as paddy fields, dry fields, and orchards.

MODES FOR CARRYING OUT THE INVENTION

The compounds included in the present invention may include the geometric isomers of an E-form and a Z-form depending on the substituents. The present invention includes the E-form, the Z-form, and a mixture of the E-form and the Z-form in any ratios. The compounds included in the present invention include optically active isomers due to the existence of one or two or more of asymmetric carbon atoms. The present invention includes all optically active isomers or racemic forms.

The compounds included in the present invention may include tautomers depending on the substituents. The present invention includes all tautomers or a mixture of the tautomers included in any ratios. For example, in the case of the compound of Formula (1): [where W is W-1; R^(1a) is hydroxy group; n, Q, R^(2a), R³, and X mean the same as described above], the following tautomers are included.

Similarly, in the case of the compound of Formula (1):

[where W is W-1; R^(1a) is —SH group; n, Q, R^(2a), R³, and X mean the same as described above], the following tautomers are included.

Among the compounds included in the present invention, the compounds that can form acid-added salt by a conventional method may form, for example, the salts of hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, and hydroiodic acid; the salts of inorganic acids such as nitric acid, sulfuric acid, phosphoric acid, chloric acid, and perchloric acid; the salts of sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; the salts of carboxylic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, fumaric acid, tartaric acid, oxalic acid, maleic acid, malic acid, succinic acid, benzoic acid, mandelic acid, ascorbic acid, lactic acid, gluconic acid, and citric acid; or the salts of amino acids such as glutamic acid and aspartic acid.

Among the compounds included in the present invention, the compounds that can form metal salt by a conventional method may form, for example, the salts of alkali metals such as lithium, sodium, and potassium; the salts of alkaline earth metals such as calcium, barium, and magnesium; or the salt of aluminum.

Specific examples of each substituent described in this specification will be described below. Here, n- means normal; i- means iso; s- means secondary; and tert-means tertiary and Ph means phenyl.

Examples of the halogen atom in this specification may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The expression of “halo” in this specification is also these halogen atoms.

The expression of C_(a-b) alkyl in this specification is a linear or a branched hydrocarbon group having a carbon atom number of a to b. Specific examples of the C_(a-b) alkyl may include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethyl propyl group, n-hexyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) cycloalkyl in this specification is a cyclic hydrocarbon group having a carbon atom number of a to b and can form a monocyclic structure or a fused ring structure of a 3-membered ring to a 6-membered ring. Each ring may be optionally substituted with an alkyl group in a range of the specified carbon atom number. Specific example of the C_(a-b) cycloalkyl may include cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) halocycloalkyl in this specification is a cyclic hydrocarbon group having a carbon atom number of a to b in which the hydrogen atom bonded to the carbon atom is optionally substituted with a halogen atom and can form a monocyclic structure or a fused ring structure of a 3-membered ring to a 10-membered ring. Each ring can be optionally substituted with an alkyl group in a range of the specified carbon atom number. The substitution position with the halogen atom may be at a ring structure part, at a side chain structure part, or at both of them. When two or more halogen atoms are used as substituents, these halogen atoms are optionally the same as or different from each other. Specific examples of the C_(a-b) halocycloalkyl may include 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, 2,2-difluoro-1-methylcyclopropyl group, 2,2-dichloro-1-methylcyclopropyl group, 2,2-dibromo-1-methylcyclopropyl group, 2,2,3,3-tetra-fluorocyclobutyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) alkenyl in this specification is a linear or a branched unsaturated hydrocarbon group having a carbon atom number of a to b and having one or two or more double bonds in the molecule. Specific examples of the C_(a-b) alkenyl may include vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 2-butenyl group, 2-methyl-2-propenyl group, 3-methyl-2-butenyl group, 1,1-dimethyl-2-propenyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) haloalkenyl in this specification is a linear or a branched unsaturated hydrocarbon group having a carbon atom number of a to b in which the hydrogen atom bonded to the carbon atom is optionally substituted with a halogen atom and having one or two or more double bonds in the molecule. In this case, when two or more halogen atoms are used as substituents, these halogen atoms are optionally the same as or different from each other. Specific examples of the C_(a-b) haloalkenyl may include 2,2-dichlorovinyl group, 2-fluoro-2-propenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-bromo-2-propenyl group, 3,3-difluoro-2-propenyl group, 2,3-dichloro-2-propenyl, 3,3-dichloro-2-propenyl group, 2,3,3-trifluoro-2-propenyl group, 2,3,3-trichloro-2-propenyl group, 1-(trifluoromethyl) ethenyl group, 4,4-difluoro-3-butenyl group, 3,4,4-trifluoro-3-butenyl group, 3-chloro-4,4,4-trifluoro-2-butenyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) cycloalkenyl in this specification is a cyclic unsaturated hydrocarbon group having a carbon atom number of a to b and having one or two or more double bonds and can form a monocyclic structure or a fused ring structure of a 3-membered ring to a 6-membered ring. Each ring can be substituted with an alkyl group in a range of the specified carbon atom number. The double bond may be either endo-form or exo-form. Specific example of the C_(a-b) cycloalkenyl may include 1-cyclopentene-1-yl group, 2-cyclopentene-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) alkynyl in this specification is a linear or a branched unsaturated hydrocarbon group having a carbon atom number of a to b and having one or two or more triple bonds in the molecule. Specific examples of the C_(a-b) alkynyl may include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butyryl group, 2-butyryl group, 3-butyryl group, 1,1-dimethyl-2-propynyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) haloalkynyl in this specification is a linear or a branched unsaturated hydrocarbon group having a carbon atom number of a to b in which the hydrogen atom bonded to the carbon atom is optionally substituted with a halogen atom and having one or two or more triple bonds in the molecule. In this case, when two or more halogen atoms are used as substituents, these halogen atoms are optionally the same as or different from each other. Specific examples of the C_(a-b) haloalkynyl may include 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) haloalkyl in this specification is a linear or a branched hydrocarbon group having a carbon atom number of a to b in which the hydrogen atom bonded to the carbon atom is optionally substituted with a halogen atom. When two or more halogen atoms are used as substituents, these halogen atoms are optionally the same as or different from each other. Specific examples of the C_(a-b) haloalkyl may include fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, a trifluoromethyl group, chlorodifluoromethyl group, trichloromethyl group, bromodifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2,2-trichloroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, heptafluoropropyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, nonafluorobutyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) alkoxy in this specification is an alkyl-O— group in which this alkyl is the above meaning alkyl group having a carbon atom number of a to b. Specific examples of the C_(a-b) alkoxy may include methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group, i-butyloxy group, s-butyloxy group, tert-butyloxy group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) alkylthio in this specification is an alkyl-S— group in which this alkyl is the above meaning alkyl group having a carbon atom number of a to b. Specific examples of the C_(a-b) alkylthio may include methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, tert-butylthio group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) alkylcarbonyl in this specification is an alkyl-C(O)— group in which this alkyl is the above meaning alkyl group having a carbon atom number of a to b. Specific examples of the C_(a-b) alkylcarbonyl may include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) haloalkylcarbonyl in this specification is a haloalkyl-C(O)— group in which this haloalkyl is the above meaning haloalkyl group having a carbon atom number of a to b. Specific examples of the C_(a-b) haloalkylcarbonyl may include fluoroacetyl group, chloroacetyl group, difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluorobutanoyl group, 3-chloro-2,2-dimethylpropanoyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) cycloalkylcarbonyl in this specification is a cycloalkyl-C(O)— group in which this cycloalkyl is the above meaning cycloalkyl group having a carbon atom number of a to b. Specific examples of the C_(a-b) cycloalkylcarbonyl may include cyclopropylcarbonyl group, 2-methylcyclopropylcarbonyl group, cyclobutylcarbonyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) halocycloalkylcarbonyl in this specification is a halocycloalkyl-C(O)— group in which this halocycloalkyl is the above meaning halocycloalkyl having a carbon atom number of a to b. Specific examples of the C_(a-b) halocycloalkylcarbonyl may include 2,2-dichlorocyclopropylcarbonyl group, 2,2-dichloro-1-methylcyclopropylcarbonyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) alkoxycarbonyl in this specification is an alkyl-O—C(O)— group in which this alkyl is the above meaning alkyl having a carbon atom number of a to b. Specific examples of the C_(a-b) alkoxycarbonyl may include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, tert-butoxycarbonyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) haloalkoxycarbonyl in this specification is a haloalkyl-O—C(O)— group in which this haloalkyl is the above meaning haloalkyl group having a carbon atom number of a to b. Specific examples of the C_(a-b) haloalkoxycarbonyl may include chloromethoxycarbonyl group, 2-chloroethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) alkylaminocarbonyl in this specification is a carbamoyl group in which one hydrogen atom is substituted with the above meaning alkyl group having a carbon atom number of a to b. Specific examples of the C_(a-b) alkylaminocarbonyl may include methylcarbamoyl group, ethylcarbamoyl group, n-propylcarbamoyl group, i-propylcarbamoyl group, n-butylcarbamoyl group, i-butylcarbamoyl group, s-butylcarbamoyl group, tert-butylcarbamoyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) haloalkylaminocarbonyl in this specification is a carbamoyl group in which one hydrogen atom is substituted with the above meaning haloalkyl group having a carbon atom number of a to b. Specific examples of the C_(a-b) haloalkylaminocarbonyl may include 2-fluoroethylcarbamoyl group, 2-chloroethylcarbamoyl group, 2,2-difluoroethylcarbamoyl group, 2,2,2-trifluoroethylcarbamoyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of di(C_(a-b) alkyl)aminocarbonyl in this specification is a carbamoyl group in which both hydrogen atoms are substituted with the above meaning alkyl groups, which are the same as or different from each other, having a carbon atom number of a to b. Specific examples of the di(C_(a-b) alkyl)aminocarbonyl may include N,N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N,N-diethylcarbamoyl group, N,N-di(n-propyl)carbamoyl group, N,N-di(n-butyl)carbamoyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) alkylaminosulfonyl in this specification is a sulfamoyl group in which one hydrogen atom is substituted with the above meaning alkyl group having a carbon atom number of a to b. Specific examples of the C_(a-b) alkylaminosulfonyl may include methylsulfamoyl group, ethylsulfamoyl group, n-propylsulfamoyl group, i-propylsulfamoyl group, n-butylsulfamoyl group, i-butylsulfamoyl group, s-butylsulfamoyl group, tert-butylsulfamoyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of di(C_(a-b) alkyl)aminosulfonyl in this specification is a sulfamoyl group in which both hydrogen atoms are substituted with the above meaning alkyl groups, which are the same as or different from each other, having a carbon atom number of a to b. Specific examples of the di(C_(a-b) alkyl)aminosulfonyl may include N,N-dimethylsulfamoyl group, N-ethyl-N-methylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-di(n-propyl)sulfamoyl group, N,N-di(n-butyl)sulfamoyl group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of C_(a-b) alkylamino in this specification is an amino group in which one hydrogen atom is substituted with the above meaning alkyl group having a carbon atom number of a to b. Specific examples of the C_(a-b) alkylamino may include methylamino group, ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, i-butylamino group, tert-butylamino group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of di(C_(a-b) alkyl)amino in this specification is an amino group in which both hydrogen atoms are substituted with the above meaning alkyl groups, which are the same as or different from each other, having a carbon atom number of a to b. Specific examples of the di(C_(a-b) alkyl)amino may include dimethylamino group, ethyl(methyl)amino group, diethylamino group, n-propyl(methyl)amino group, i-propyl(methyl)amino group, di(n-propyl)amino group, di(n-butyl)amino group and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of (C_(a-b)) alkyl optionally substituted with R⁶, (C_(a-b)) alkyl optionally substituted with R²⁷, (C_(a-b)) alkyl optionally substituted with R³⁴, (C_(a-b)) alkyl optionally substituted with R³⁵, or (C_(a-b)) alkyl optionally substituted with R³⁶ in this specification is the above meaning alkyl group having a carbon atom number of a to b in which the hydrogen atoms bonded to the carbon atoms are optionally substituted with any R⁶, R²⁷, R³⁴, R³⁵, or R³⁶. Each of these groups is selected in a range of the specified carbon atom number. In this case, when two or more of substituents R⁶, R²⁷, R³⁴, R³⁵, or R³⁶ are contained in the (C_(a-b)) alkyl group, R⁶, R²⁷, R³⁴, R³⁵, or R³⁶ are optionally the same as or different from each other.

The expression of (C_(a-b)) cycloalkyl optionally substituted with R⁶ or (C_(a-b)) cycloalkyl optionally substituted with R²⁷ in this specification is the above meaning cycloalkyl group having a carbon atom number of a to b in which the hydrogen atoms bonded to the carbon atoms are optionally substituted with any R⁶ or R²⁷. Each of these groups is selected in a range of the specified carbon atom number. In this case, when two or more of substituents R⁶ or R²⁷ are contained in the (C_(a-b)) cycloalkyl group, R⁶ or R²⁷ are optionally the same as or different from each other. The substituted positions may be at a ring structure part, at a side chain structure part, or at both of them.

Specific examples of the expression of “R¹¹ optionally forms a 3-7-membered ring together with a nitrogen atom to which R¹¹ and R¹² are bonded by forming a C₂₋₆ alkylene chain together with R¹², and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)₂, or N(R³³) and is optionally substituted with an oxo group or a thioxo group”, “R^(11a) optionally forms a 3-7-membered ring together with a nitrogen atom to which R^(11a) and R^(12a) are bonded by forming a C₂₋₆ alkylene chain together with R^(12a), and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)₂, or N(R³³) and is optionally substituted with an oxo group or a thioxo group”, and “R²¹ optionally forms a 3-7-membered ring together with a nitrogen atom to which R²¹ and R²² are bonded by forming a C₂₋₆ alkylene chain together with R²², in this case, the alkylene chain optionally contains one O, S, S(O), S(O)₂, or N(R³⁹) and is optionally substituted with an oxo group or a thioxo group” in this specification may include aziridine, azetidine, azetidin-2-one, pyrrolidin, pyrrolidin-2-one, oxazolidine, oxazolidin-2-one, oxazolidin-2-thione, thiazolidine, thiazolidin-2-one, thiazolidin-2-thione, imidazolidine, imidazolidin-2-one, imidazolidin-2-thione, piperidine, piperidin-2-one, piperidin-2-thione, 2H-3,4,5,6-tetrahydro-1,3-oxazin-2-one, 2H-3,4,5,6-tetrahydro-1,3-oxazine-2-thione, morpholine, 2H-3,4,5,6-tetrahydro-1,3-thiazin-2-one, 2H-3,4,5,6-tetrahydro-1,3-thiazin-2-thione, thiomorpholine, thiomorpholine-1-oxide, thiomorpholine-1,1-dioxide, perhydropyrimidin-2-one, piperazine, homopiperidine, homopiperidin-2-one, heptamethyleneimine and the like. Each of these groups is selected in a range of the specified carbon atom number.

The expression of (C_(a-b) alkoxy) C_(d-e) alkyl, (C_(a-b) alkylthio) C_(d-e) alkyl, or the like in this specification is a linear or a branched hydrocarbon group having a carbon atom number of d to e in which the hydrogen atom bonded to the carbon atom is optionally substituted with the any above meaning C_(a-b) alkoxy group or C_(a-b) alkylthio group respectively. Each of these groups is selected in a range of the specified carbon atom number.

The “5-6-membered aromatic heterocycle” in this specification means a monocyclic aromatic heterocycle in which the number of atoms forming the ring is 5 to 6 and 1 to 5 hetero atoms (the hetero atom means a nitrogen atom, an oxygen atom, or a sulfur atom) are contained in the atoms forming the ring. Specific examples of the 5-6-membered aromatic heterocycle may include pyrrole, pyrazole, imidazole, triazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, furan, thiophene, thiazole, isothiazole, oxazole, isoxazole, oxadiazole, thiadiazole and the like.

When the “5-6-membered aromatic heterocycle” contains a C═N double bond, the nitrogen atom may be N-oxide.

The “5-6-membered heteroaryl” in this specification means a monovalent substituent formed by removing one hydrogen atom from any position in the above meaning “5-6-membered aromatic heterocycle”. Positions to which these substituents are bonded are not particularly limited and the substituents may be bonded to desired positions.

The “3-7-membered non-aromatic heterocycle” in this specification means a monocyclic non-aromatic heterocycle having the following characteristics:

1) the number of atoms forming the ring is 3 to 7,

2) 1 to 3 hetero atoms (the hetero atom means a nitrogen atom, an oxygen atom, or a sulfur atom) are contained in the atoms forming the ring,

3) a carbonyl group, a thiocarbonyl group, a double bond, or a triple bond may be contained in the ring, and

4) when a sulfur atom is contained in the atoms forming the ring, the sulfur atom may be a sulfinyl group or a sulfonyl group.

Specific examples of the 3-7-membered non-aromatic heterocycle may include azetidine, pyrrolidine, pyrrolidinone, oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, piperazine, piperazinone, piperidine, piperidinone, morpholine, thiomorpholine, azepine, diazepine, oxetane, tetrahydrofuran, 1,3-dioxolane, tetrahydropyran, 1,4-dioxane, oxepane, homomorpholine and the like.

The “3-7-membered heterocyclyl” in this specification means a monovalent substituent formed by removing one hydrogen atom from any position in the above meaning “3-7-membered non-aromatic heterocycle”. Positions to which these substituents are bonded are not particularly limited and the substituents may be bonded to desired positions.

The “5-6-membered heteroaryl optionally substituted with R²⁸ and R^(28a)” in this specification is a “5-6-membered heteroaryl” in which the hydrogen atoms on the carbon atoms forming the ring of the “5-6-membered heteroaryl” are substituted on the carbon atoms with any R²⁸ in a range of the number of the existing hydrogen atoms. In this case, when nitrogen exists among the atoms forming the ring of the “5-6-membered heteroaryl” and the nitrogen atom potentially has a NH structure, the “5-6-membered heteroaryl optionally substituted with R²⁸ and R^(28a)” is a “5-6-membered heteroaryl” in which the hydrogen atom on the nitrogen atom is optionally substituted on the nitrogen atom with any R^(28a) in a range of the number of existing hydrogen atoms. In this case, when two or more substituents R²⁸ on the carbon atoms forming the ring of the “5-6-membered heteroaryl” and two or more substituents R^(28a) substituted with the nitrogen atom potentially having a NH structure forming the ring independently exist, two or more of each of R²⁸ and R^(28a) are optionally the same as or different from each other, and when two R²⁸ are adjacent, the two adjacent R²⁸ optionally form a 6-membered ring together with carbon atoms to which each R²⁸ is bonded by forming —CH═CH—CH═CH—.

The “3-7-membered heterocyclyl optionally substituted with R²⁸ and R^(28a)” in this specification is a “3-7-membered heterocyclyl” in which the hydrogen atoms on the carbon atoms forming the ring of the “3-7-membered heterocyclyl” are substituted on the carbon atoms with any R²⁸ in a range of the number of the existing hydrogen atoms. In this case, when nitrogen exists among the atoms forming the ring of the “3-7-membered heterocyclyl” and the nitrogen atom potentially has a NH structure, the “3-7-membered heterocyclyl optionally substituted with R^(28a)” is a “3-7-membered heterocyclyl” in which the hydrogen atom on the nitrogen atom is optionally substituted on the nitrogen atom with any R^(28a) in a range of the number of existing hydrogen atoms. In this case, when two or more substituents R²⁸ on the carbon atoms forming the ring of the “3-7-membered heterocyclyl” and two or more substituents R^(28a) substituted with the nitrogen atom potentially having a NH structure forming the ring independently exist, two or more of each of R²⁸ and R^(28a) are optionally the same as or different from each other, and when two R²⁸ are adjacent, the two adjacent R²⁸ optionally form a 6-membered ring together with carbon atoms to which each R²⁸ is bonded by forming —CH═CH—CH═CH—.

Next, the production method of the compound of the present invention will be described below.

Production Method A

The heterocyclic amide compound of Formula (1) can be produced by, for example, reacting the compound of Formula (2) with the compound of Formula (3a).

The compound of Formula (1): [where Q and R³, W, and X mean the same as defined above] of the present invention can be produced by reacting the compound of Formula (2): [where Q and R³ mean the same as defined above] or the salt thereof with the compound of Formula (3a): [where W and X mean the same as defined above] or the salt thereof in a solvent or without using a solvent by using a base, a condensing agent, and/or a catalyst if necessary and adding an additive if necessary.

In this reaction, the compound of Formula (3a) can be used in a range of 0.1 equivalents to 100 equivalents relative to 1 equivalent of the compound of Formula (2).

When the solvent is used, the solvent to be used may be a solvent that is inactive to the reaction. Example of the solvent may include polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dimethylsulfoxide, and 1,3-dimethyl-2-imidazolinone; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, and diphenyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane; and aliphatic hydrocarbons such as n-pentane and n-hexane. These solvents may be used singly or in combination of two or more of them.

When the base is used, examples of the base to be used may include organic bases such as triethylamine, pyridine, and 4-(dimethylamino)pyridine and inorganic bases such as potassium carbonate and sodium carbonate. These bases may be used in a range of 0.1 equivalents to 50 equivalents relative to 1 equivalent of the compound of Formula (2).

When the condensing agent is used, examples of the condensing agent to be used may include 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N′-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 2-chloro-1-methylpyridinium iodide. These condensing agents may be used in a range of 0.1 equivalents to 50 equivalents relative to 1 equivalent of the compound of Formula (2).

When the additive is used, examples of the additive to be used may include 3H-[1,2,3]triazolo[4,5-b]pyridine-3-ol and 1-hydroxybenzotriazole. These additives may be used in a range of 0.1 equivalents to 50 equivalents relative to 1 equivalent of the compound of Formula (2).

As the reaction temperature, any temperature from −78° C. to the reflux temperature of the reaction mixture can be set. Although the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, usually any time may be set in a range of 5 minutes to 100 hours.

Some of the compounds of Formula (2) are known compounds and some of the compounds are commercially available.

Some of the compounds of Formula (3a) are known compounds and can be synthesized in accordance with known methods described in documents. Examples of the methods known in the documents may include a method described in WO 2008/006540 Pamphlet.

Production Method B

The heterocyclic amide compound of Formula (1) can be produced by, for example, reacting the compound of Formula (2) with the compound of Formula (3b).

The compound of Formula (1): [where Q and R³, W, and X mean the same as defined above] of the present invention can be produced by reacting the compound of Formula (2): [where Q and R³ mean the same as defined above] or the salt thereof with the compound of Formula (3b): [where W and X mean the same as defined above and X^(a) is a leaving group such as a halogen atom] or the salt thereof in a solvent or without using a solvent by using a base if necessary.

In this reaction, the compound of Formula (3b) can be used in a range of 0.1 equivalents to 100 equivalents relative to 1 equivalent of the compound of Formula (2).

When the solvent is used, the solvent to be used may be a solvent that is inactive to the reaction. Example of the solvent may include polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dimethylsulfoxide, and 1,3-dimethyl-2-imidazolinone; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, and diphenyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane; and aliphatic hydrocarbons such as n-pentane and n-hexane. These solvents may be used singly or in combination of two or more of them.

When the base is used, examples of the base to be used may include organic bases such as triethylamine, pyridine, and 4-(dimethylamino)pyridine and inorganic bases such as potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, and sodium hydride. These bases may be used in a range of 0.1 equivalents to 50 equivalents relative to 1 equivalent of the compound of Formula (2). These bases may be used singly or in combination of two or more of them.

As the reaction temperature, any temperature from −78° C. to the reflux temperature of the reaction mixture can be set. Although the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, usually any time may be set in a range of 5 minutes to 100 hours.

Production Method C

The compound of Formula (1-2): [where W, Q and R³ mean the same as defined above] of the present invention can be produced, for example, by reacting the compound of Formula (1-1): [where W, Q and R³ mean the same as defined above] of the present invention with sulfidizing agents such as phosphorus pentasulfide, phosphorus pentasulfide-HMDO (hexamethyldisiloxane), and Lawesson{hacek over (s)} reagent (2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide).

The sulfidizing agent used in this reaction can be used in a range of 0.5 equivalents to 50 equivalents relative to 1 equivalent of the compound of Formula (1-1).

Bases such as potassium carbonate, triethylamine, pyridine, and 4-(dimethylamino)pyridine can be used if necessary.

This reaction can be carried out without using a solvent. However, a solvent may be used. Examples of the solvent may include polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dimethylsulfoxide, 1,3-dimethyl-2-imidazolinone, and water; alcohols such as methanol, ethanol, propanol, 2-propanol, and ethylene glycol; ethers such as diethyl ether, tetrahydrofuran, and diphenyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; and aliphatic hydrocarbons such as pentane and n-hexane. These solvents may be used singly or in combination of two or more of them.

As the reaction temperature, any temperature from −60° C. to the reflux temperature of the reaction mixture can be set. Although the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, usually any time may be set in a range of 5 minutes to 100 hours.

In the production method A to the production method C, usual post treatment of the reaction mixture after completion of the reaction such as direct concentration, concentration after dissolving in an organic solvent and washing with water, or concentration after pouring into ice-water and extracting with an organic solvent can give the compound of the present invention. When purification is required, the compound can be separated and purified by any purification method such as recrystallization, column chromatography, thin layer chromatography, and liquid chromatography.

Some of the compound of Formula (3b) can be synthesized in accordance with the reaction formula 1 described below.

Production Method D

The heterocyclic amide compound of Formula (1-1) can be produced by, for example, reacting the compound of Formula (1-3): [where W and Q mean the same as defined above] with the compound of Formula (4): [where R³ has the same as defined above and J is a leaving group such as a halogen atom, —OH, —OSO₂Me, and —OSO₂CF₃].

In this reaction, the compound of Formula (4) can be used in a range of 0.5 equivalents to 50 equivalents relative to 1 equivalent of the compound of Formula (1-3). Acids such as hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid or bases such as potassium carbonate, triethylamine, pyridine, and 4-(dimethylamino)pyridine, sodium hydride, sodium hydroxide, and potassium hydroxide can be used if necessary. Alternatively, Mitsunobu reaction using diethyl azodicarboxylate, triphenylphosphine, and the like can be used.

This reaction can be carried out without using a solvent. However, a solvent may be used. Example of the solvent may include polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dimethylsulfoxide, 1,3-dimethyl-2-imidazolinone, and water; alcohols such as methanol, ethanol, propanol, 2-propanol, and ethylene glycol; ethers such as diethyl ether, tetrahydrofuran, and diphenyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; and aliphatic hydrocarbons such as pentane and n-hexane. These solvents may be used singly or in combination of two or more of them.

As the reaction temperature, any temperature from −60° C. to the reflux temperature of the reaction mixture can be set. Although the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, usually any time may be set in a range of 5 minutes to 100 hours.

Some of the compounds of Formula (4) are known compounds and some of the compounds are commercially available. Compounds other than the compounds described above can be synthesized in accordance with methods described in reference documents.

Reaction Formula 1

The compound of Formula (3b) can be produced by, for example, reacting the compound of Formula (3a) with a halogenating agent.

The compound of Formula (3b): [where W, X and X^(a) mean the same as defined above] can be produced by reacting the compound of Formula (3a) [where W and X mean the same as defined above] or the salt thereof with the halogenating agent in a solvent or without using a solvent by using a base if necessary.

Examples of the halogenating agent may include thionyl chloride, oxalyl chloride, and phosphoryl chloride. The halogenating agent can be used in a range of 0.1 equivalents to 100 equivalents relative to 1 equivalent of the compound of Formula (3a).

When the solvent is used, the solvent to be used may be a solvent that is inactive to the reaction. Example of the solvent may include polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dimethylsulfoxide, and 1,3-dimethyl-2-imidazolinone; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, and diphenyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane; and aliphatic hydrocarbons such as n-pentane and n-hexane. These solvents may be used singly or in combination of two or more of them.

When the base is used, examples of the base to be used may include organic bases such as triethylamine, pyridine, and 4-(dimethylamino)pyridine and inorganic bases such as potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, and sodium hydride. These bases may be used in a range of 0.1 equivalents to 50 equivalents relative to 1 equivalent of the compound of Formula (3a). These bases may be used singly or in combination of two or more of them.

As the reaction temperature, any temperature from −78° C. to the reflux temperature of the reaction mixture can be set. Although the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, usually any time may be set in a range of 5 minutes to 100 hours.

The usual post treatment for the reaction mixture after completion of the reaction can give a production intermediate serving as a starting material compound for the production method B.

The production intermediate produced by this method can be used in the following step without isolation and purification.

Specific examples of the active compound included in the present invention may include the compounds listed in First Table to Third Table. The compounds listed in First Table to Third Table, however, are compounds for exemplification, and thus the present invention is not limited to these compounds. In Tables, the substituent described as Me is methyl group. Similarly in Tables, Et is ethyl group, n-Pr and Pr-n are each normal-propyl group, i-Pr and Pr-i are each iso-propyl group, c-Pr and Pr-c are each cyclopropyl group, n-Bu and Bu-n are each normal-butyl group, s-Bu and Bu-s are each secondary-butyl group, an i-Bu and Bu-i are each iso-butyl group, t-Bu and Bu-t are each tertiary-butyl group, c-Bu and Bu-c are each cyclobutyl group, n-Pen and Pen-n are each normal-pentyl group, i-Pen and Pen-i are each iso-pentyl group, s-Pen and Pen-s are each secondary-pentyl group, t-Pen and Pen-t are each tertiary-pentyl group, c-Pen and Pen-c are each cyclopentyl group, 3-Pen is —CH(Et)₂ group, n-Hex and Hex-n are each normal-hexyl group, c-Hex and Hex-c are each cyclohexyl, and Ph is phenyl group.

In Tables, structures of D-3, D-3a, D-4, D-4a, D-4b, D-8, D-8a, D-8b, D-8c, D-8d, D-8e, D-8f, D-8g, D-8h, D-9, D-9a, D-9b, D-9c, D-9d, D-9e, D-9f, D-9g, D-9h, D-9i, D-9j, D-9k, D-9m, D-10a, D-11, D-12, D-13a, D-14, D-15, D-16, D-16a, D-16b, D-16c, D-16d, D-16e, D-16f, D-16g, D-16h, D-16i, D-16j, D-16k, D-16m, D-16n, D-16p, D-17, D-17a, D-17b, D-18, D-19, D-21, D-24a, D-24b, D-24c, D-24d, D-24e and D-24f are the following structures.

FIRST TABLE

TABLE 1 R^(1a) R^(1a) R^(1a) H CH₂CF₃ C(Me)₂CH₂CN F (CH₂)₃Cl CH₂Pr-c Cl (CH₂)₃Br CH₂(D-16) Br (CH₂)₂CF₃ CH₂(D-16d) I CHFCH₃ CH₂Bu-c Me CF₂CH₃ CH₂Pen-c Et CF(CH₃)₂ CH₂Hex-c Pr-n CF₂CF₂H CH(Me)Pr-c Pr-i CF₂CF₃ CH(Me)(D-16) Pr-c CF₂CF₂CF₃ CH(Me)(D-16e) Bu-n CF(CF₃) CH(Me)Bu-c Bu-i CH(Me)Cl CH(Me)Pen-c Bu-c CH(Me)Br CH(Me)Hex-c Bu-s CH(Et)Cl (CH₂)₂Pr-c Bu-t CH(Et)Br (CH₂)₂(D-16) Pen-n CH(Pr-n)Cl (CH₂)₂(D-16e) Pen-i CH(Pr-n)Br (CH₂)₂Bu-c Pen-c CH(Pr-i)Cl (CH₂)₂Pen-c Pen-s CH(Pr-i)Br (CH₂)₂Hex-c Pen-t C(Me)₂Cl CH₂OMe 3-Pen C(Me)₂Br CH₂OEt Hex-n CH(Me)CH₂Cl CH₂OPr-n Hex-c CH(Me)CH₂Br CH₂OPr-i CH₂Cl C(Me)₂CH₂Cl CH₂OBu-n CH₂Br C(Me)₂CH₂Br CH₂OBu-i CHBr₂ CH₂CN CH₂OBu-s CF₂H (CH₂)₂CN CH₂OBu-t CF₂Cl (CH₂)₃CN CH₂OPen-n CF₂Br CH(Me)CN CH₂OPen-i CF₃ CH(Et)CN CH₂OPen-s (CH₂)₂Cl CH(Pr-n)CN CH₂OPen-t (CH₂)₂Br CH(Pr-i)CN CH₂OHex-n CH₂CF₂H C(Me)₂CN CH(Me)OMe CH₂CF₂Cl CH(Me)CH₂CN CH(Me)OEt CH₂CF₂Br CH(Et)CH₂CN CH(Me)OPr-n

TABLE 2 R^(1a) R^(1a) R^(1a) CH(Me)OPr-i C(Me)₂OBu-n CH₂O(CH₂)₂Cl CH(Me)OBu-n C(Me)₂OBu-i CH₂O(CH₂)₂Br CH(Me)OBu-i C(Me)₂OBu-s CH(Me)OCF₂H CH(Me)OBu-s C(Me)₂OBu-t CH(Me)OCF₃ CH(Me)OBu-t (CH₂)₂OMe CH(Me)OCH₂CF₂H CH(Me)OPen-n (CH₂)₂OEt CH(Me)OCH₂CF₃ CH(Me)OPen-i (CH₂)₂OPr-n CH(Me)O(CH₂)₂CF₃ CH(Me)OPen-s (CH₂)₂OPr-i CH(Me)O(CH₂)₂Cl CH(Me)OPen-t (CH₂)₂OBu-n CH(Me)O(CH₂)₂Br CH(Me)OHex-n (CH₂)₂OBu-i CH(Et)OCF₂H CH(Et)OMe (CH₂)₂OBu-s CH(Et)OCF₃ CH(Et)OEt (CH₂)₂OBu-t CH(Et)OCH₂CF₂H CH(Et)OPr-n CH(Me)CH₂OMe CH(Et)OCH₂CF₃ CH(Et)OPr-i CH(Me)CH₂OEt CH(Et)O(CH₂)₂CF₃ CH(Et)OBu-n CH(Me)CH₂OPr-n CH(Et)O(CH₂)₂Cl CH(Et)OBu-i CH(Me)CH₂OPr-i CH(Et)O(CH₂)₂Br CH(Et)OBu-s CH(Me)CH₂OBu-n C(Me)₂OCF₂H CH(Et)OBu-t CH(Me)CH₂OBu-i C(Me)₂OCF₃ CH(Et)OPen-n CH(Me)CH₂OBu-s C(Me)₂OCH₂CF₂H CH(Et)OPen-i CH(Me)CH₂OBu-t C(Me)₂OCH₂CF₃ CH(Et)OPen-s CH(Et)CH₂OMe C(Me)₂O(CH₂)₂CF₃ CH(Et)OPen-t CH(Et)CH₂OEt C(Me)₂O(CH₂)₂Cl CH(Et)OHex-n (CH₂)₃OMe C(Me)₂O(CH₂)₂Br CH(Pr-n)OMe (CH₂)₃OEt (CH₂)₂OCF₃ CH(Pr-n)OEt (CH₂)₃OPr-n (CH₂)₂OCH₂CF₂H CH(Pr-n)OPr-n (CH₂)₃OPr-i (CH₂)₂OCH₂CF₃ CH(Pr-n)OPr-i (CH₂)₃OBu-n (CH₂)₂O(CH₂)₂Cl CH(Pr-i)OMe (CH₂)₃OBu-i (CH₂)₂O(CH₂)₂Br CH(Pr-i)OEt (CH₂)₃OBu-s CH₂OH CH(Pr-i)OPr-n (CH₂)₃OBu-t CH(Me)OH CH(Pr-i)OPr-i CH₂OCF₂H CH(Et)OH C(Me)₂OMe CH₂OCF₃ CH(iPr)OH C(Me)₂OEt CH₂OCH₂CF₂H C(Me)₂OH C(Me)₂OPr-n CH₂OCH₂CF₃ (CH₂)₂OH C(Me)₂OPr-i CH₂O(CH₂)₂CF₃ CH(Me)CH₂OH

TABLE 3 R^(1a) R^(1a) R^(1a) (CH₂)₃OH C(Me)₂O(CH₂)₂OPr-n CH(Me)OC(O)Pr-i CH₂OCH₂OMe C(Me)₂O(CH₂)₂OPr-i CH(Et)OC(O)Me CH₂OCH₂OEt (CH₂)₂OCH₂OMe CH(Et)OC(O)Et CH₂OCH₂OPr-n (CH₂)₂OCH₂OEt CH(Et)OC(O)Pr-i CH₂OCH₂OPr-i (CH₂)₂OCH₂OPr-n CH₂OPh CH₂O(CH₂)₂OMe (CH₂)₂OCH₂OPr-i CH(Me)OPh CH₂O(CH₂)₂OEt (CH₂)₂O(CH₂)₂OMe CH₂C(O)OH CH₂O(CH₂)₂OPr-n (CH₂)₂O(CH₂)₂OEt CH₂C(O)OMe CH₂O(CH₂)₂OPr-i (CH₂)₂O(CH₂)₂OPr-n CH₂C(O)OEt CH₂OCH(Me)CH₂OMe (CH₂)₂O(CH₂)₂OPr-i CH₂C(O)OPr-n CH₂OCH(Me)CH₂OEt CH(Me)CH₂OCH₂OMe CH₂C(O)OPr-i CH₂OCH₂CH(Me)OMe CH(Me)CH₂OCH₂OEt CH₂C(O)OBu-n CH₂OCH₂CH(Me)OEt CH(Me)CH₂O(CH₂)₂OMe CH₂C(O)OBu-i CH₂OCH(Me)OMe CH(Me)CH₂O(CH₂)₂OEt CH₂C(O)OBu-s CH₂OCH(Me)OEt CH(Et)CH₂OCH₂OMe CH₂C(O)OBu-t CH₂O(CH₂)₃OMe CH(Et)CH₂OCH₂OEt CH₂C(O)OPen-n CH₂O(CH₂)₃OEt CH(Et)CH₂O(CH₂)₂OMe CH₂C(O)OPen-i CH(Me)OCH₂OMe CH(Et)CH₂O(CH₂)₂OEt CH₂C(O)OPen-s CH(Me)OCH₂OEt CH(Et)O(CH₂)₂OMe CH₂C(O)OPen-t CH(Me)OCH₂OPr-n CH(Et)O(CH₂)₂OEt CH₂C(O)OHex-n CH(Me)OCH₂OPr-i CH(Et)O(CH₂)₂OPr-n CH₂C(O)OCH₂OMe CH(Me)O(CH₂)₂OMe CH(Et)O(CH₂)₂OPr-i CH₂C(O)O(CH₂)₂OMe CH(Me)O(CH₂)₂OEt CH(Pr-n)O(CH₂)₂OMe CH₂C(O)O(CH₂)₂OEt CH(Me)O(CH₂)₂OPr-n CH(Pr-n)O(CH₂)₂OEt CH₂C(O)O(CH₂)₂OPr-i CH(Me)O(CH₂)₂OPr-i CH(Pr-n)O(CH₂)₂OPr-n CH₂C(O)NHMe CH(Me)OCH(Me)CH₂OMe CH(Pr-n)O(CH₂)₂OPr-i CH₂C(O)NHEt CH(Me)OCH(Me)CH₂OEt CH(Pr-i)O(CH₂)₂OMe CH₂C(O)NHPr-n CH(Me)OCH₂CH(Me)OMe CH(Pr-i)O(CH₂)₂OEt CH₂C(O)NHPr-i CH(Me)OCH₂CH(Me)OEt CH(Pr-i)O(CH₂)₂OPr-n CH(Me)C(O)OH C(Me)₂OCH₂OMe CH(Pr-i)O(CH₂)₂OPr-i CH(Me)C(O)OMe C(Me)₂OCH₂OEt CH₂OC(O)Me CH(Me)C(O)OEt C(Me)₂OCH₂OPr-n CH₂OC(O)Et CH(Me)C(O)OPr-i C(Me)₂OCH₂OPr-i CH₂OC(O)Pr-i CH(Me)C(O)OCH₂OMe C(Me)₂O(CH₂)₂OMe CH(Me)OC(O)Me CH(Me)C(O)O(CH₂)₂OMe C(Me)₂O(CH₂)₂OEt CH(Me)OC(O)Et CH(Me)C(O)O(CH₂)₂OEt

TABLE 4 R^(1a) R^(1a) R^(1a) CH(Me)C(O)O(CH₂)₂OPr-i CH₂S(O)₂Pr-i CH(Me)SPr-i CH(Me)C(O)NHMe CH₂SBu-n CH(Me)S(O)Pr-i CH(Me)C(O)NHEt CH₂S(O)Bu-n CH(Me)S(O)₂Pr-i CH(Me)C(O)NHPr-n CH₂S(O)₂Bu-n CH(Me)SBu-n CH(Me)C(O)NHPr-i CH₂SBu-i CH(Me)S(O)Bu-n CH(Et)C(O)OH CH₂S(O)Bu-i CH(Me)S(O)₂Bu-n CH(Et)C(O)OMe CH₂S(O)₂Bu-i CH(Me)SBu-i CH(Et)C(O)OEt CH₂SBu-s CH(Me)S(O)Bu-i CH(Et)C(O)OPr-i CH₂S(O)Bu-s CH(Me)S(O)₂Bu-i CH(Et)C(O)OCH₂OMe CH₂S(O)₂Bu-s CH(Me)SBu-s CH(Et)C(O)O(CH₂)₂OMe CH₂SBu-t CH(Me)S(O)Bu-s CH(Et)C(O)O(CH₂)₂OEt CH₂S(O)Bu-t CH(Me)S(O)₂Bu-s CH(Et)C(O)O(CH₂)₂OPr-i CH₂S(O)₂Bu-t CH(Me)SBu-t CH(Et)C(O)NHMe CH₂SPen-n CH(Me)S(O)Bu-t CH(Et)C(O)NHEt CH₂S(O)Pen-n CH(Me)S(O)₂Bu-t (CH₂)₂C(O)OH CH₂S(O)₂Pen-n CH(Me)SPen-n (CH₂)₂C(O)OMe CH₂SPen-i CH(Me)S(O)Pen-n (CH₂)₂C(O)OEt CH₂S(O)Pen-i CH(Me)S(O)₂Pen-n (CH₂)₂C(O)O(CH₂)₂OMe CH₂S(O)₂Pen-i CH(Me)SPen-i (CH₂)₂C(O)O(CH₂)₂OEt CH₂SPen-s CH(Me)S(O)Pen-i (CH₂)₂C(O)NHMe CH₂S(O)Pen-s CH(Me)S(O)₂Pen-i (CH₂)₂C(O)NHEt CH₂S(O)₂Pen-s CH(Me)SPen-s (CH₂)₂C(O)NHPr-n CH₂SPen-t CH(Me)S(O)Pen-s (CH₂)₂C(O)NHPr-i CH₂S(O)Pen-t CH(Me)S(O)₂Pen-s CH₂SMe CH₂S(O)₂Pen-t CH(Me)SPen-t CH₂S(O)Me CH₂SHex-n CH(Me)S(O)Pen-t CH₂S(O)₂Me CH(Me)SMe CH(Me)S(O)₂Pen-t CH₂SEt CH(Me)S(O)Me CH(Me)SHex-n CH₂S(O)Et CH(Me)S(O)₂Me C(Me)₂SMe CH₂S(O)₂Et CH(Me)SEt C(Me)₂S(O)Me CH₂SPr-n CH(Me)S(O)Et C(Me)₂S(O)₂Me CH₂S(O)Pr-n CH(Me)S(O)₂Et C(Me)₂SEt CH₂S(O)₂Pr-n CH(Me)SPr-n C(Me)₂S(O)Et CH₂SPr-i CH(Me)S(O)Pr-n C(Me)₂S(O)₂Et CH₂S(O)Pr-i CH(Me)S(O)₂Pr-n C(Me)₂SPr-n

TABLE 5 R^(1a) R^(1a) R^(1a) C(Me)₂S(O)Pr-n (CH₂)₂SPr-n C(Me)₂CH₂S(O)₂Et C(Me)₂S(O)₂Pr-n (CH₂)₂S(O)Pr-n C(Me)₂CH₂SPr-n C(Me)₂SPr-i (CH₂)₂S(O)₂Pr-n C(Me)₂CH₂S(O)Pr-n C(Me)₂S(O)Pr-i (CH₂)₂SPr-i C(Me)₂CH₂S(O)₂Pr-n C(Me)₂S(O)₂Pr-i (CH₂)₂S(O)Pr-i C(Me)₂CH₂SPr-i C(Me)₂SBu-n (CH₂)₂S(O)₂Pr-i C(Me)₂CH₂S(O)Pr-i C(Me)₂S(O)Bu-n (CH₂)₃SMe C(Me)₂CH₂S(O)₂Pr-i C(Me)₂S(O)₂Bu-n (CH₂)₃(O)Me CH(Et)SMe C(Me)₂SBu-i (CH₂)₃S(O)₂Me CH(Et)S(O)Me C(Me)₂S(O)Bu-i (CH₂)₃SEt CH(Et)S(O)₂Me C(Me)₂S(O)₂Bu-i (CH₂)₃S(O)Et CH(Et)SEt C(Me)₂SBu-s (CH₂)₃S(O)₂Et CH(Et)S(O)Et C(Me)₂S(O)Bu-s CH(Me)CH₂SMe CH(Et)S(O)₂Et C(Me)₂S(O)₂Bu-s CH(Me)CH₂S(O)Me CH(Et)SPr-n C(Me)₂SBu-t CH(Me)CH₂S(O)₂Me CH(Et)S(O)Pr-n C(Me)₂S(O)Bu-t CH(Me)CH₂SEt CH(Et)S(O)₂Pr-n C(Me)₂S(O)₂Bu-t CH(Me)CH₂S(O)Et CH(Et)SPr-i C(Me)₂SPen-n CH(Me)CH₂S(O)₂Et CH(Et)S(O)Pr-i C(Me)₂S(O)Pen-n CH(Me)CH₂SPr-n CH(Et)S(O)₂Pr-i C(Me)₂S(O)₂Pen-n CH(Me)CH₂S(O)Pr-n CH(Pr-n)SMe C(Me)₂SPen-i CH(Me)CH₂S(O)₂Pr-n CH(Pr-n)S(O)Me C(Me)₂S(O)Pen-i CH(Me)CH₂SPr-i CH(Pr-n)S(O)₂Me C(Me)₂S(O)₂Pen-i CH(Me)CH₂S(O)Pr-i CH(Pr-n)SEt C(Me)₂SPen-s CH(Me)CH₂S(O)₂Pr-i CH(Pr-n)S(O)Et C(Me)₂S(O)Pen-s CH(Et)CH₂SMe CH(Pr-n)S(O)₂Et C(Me)₂S(O)₂Pen-s CH(Et)CH₂S(O)Me CH(Pr-n)SPr-n C(Me)₂SPen-t CH(Et)CH₂S(O)₂Me CH(Pr-n)S(O)Pr-n C(Me)₂S(O)Pen-t CH(Et)CH₂SEt CH(Pr-n)S(O)₂Pr-n C(Me)₂S(O)₂Pen-t CH(Et)CH₂S(O)Et CH(Pr-n)SPr-i (CH₂)₂SMe CH(Et)CH₂S(O)₂Et CH(Pr-n)S(O)Pr-i (CH₂)₂S(O)Me C(Me)₂CH₂SMe CH(Pr-n)S(O)₂Pr-i (CH₂)₂S(O)₂Me C(Me)₂CH₂S(O)Me CH(Pr-i)SMe (CH₂)₂SEt C(Me)₂CH₂S(O)₂Me CH(Pr-i)S(O)Me (CH₂)₂S(O)Et C(Me)₂CH₂SEt CH(Pr-i)S(O)₂Me (CH₂)₂S(O)₂Et C(Me)₂CH₂S(O)Et CH(Pr-i)SEt

TABLE 6 R^(1a) R^(1a) R^(1a) CH(Pr-i)S(O)Et CH₂SCF(CF₃)₂ C(Me)₂S(O)(CH₂)₂CF₃ CH(Pr-i)S(O)₂Et CH(Me)SCF₂H C(Me)₂S(O)₂(CH₂)₂CF₃ CH(Pr-i)SPr-n CH(Me)S(O)CF₂H C(Me)₂S(CH₂)₂Cl CH(Pr-i)S(O)Pr-n CH(Me)S(O)₂CF₂H C(Me)₂S(O)(CH₂)₂Cl CH(Pr-i)S(O)₂Pr-n CH(Me)SCF₃ C(Me)₂S(O)₂(CH₂)₂Cl CH(Pr-i)SPr-i CH(Me)S(O)CF₃ C(Me)₂S(CH₂)₂Br CH(Pr-i)S(O)Pr-i CH(Me)S(O)₂CF₃ C(Me)₂S(O)(CH₂)₂Br CH(Pr-i)S(O)₂Pr-i CH(Me)SCH₂CF₂H C(Me)₂S(O)₂(CH₂)₂Br CH₂SCF₂H CH(Me)S(O)CH₂CF₂H (CH₂)₂SCF₃ CH₂S(O)CF₂H CH(Me)S(O)₂CH₂CF₂H (CH₂)₂S(O)CF₃ CH₂S(O)₂CF₂H CH(Me)SCH₂CF₃ (CH₂)₂S(O)₂CF₃ CH₂SCF₃ CH(Me)S(O)CH₂CF₃ (CH₂)₂SCH₂CF₂H CH₂S(O)CF₃ CH(Me)S(O)₂CH₂CF₃ (CH₂)₂S(O)CH₂CF₂H CH₂S(O)₂CF₃ CH(Me)S(CH₂)₂CF₃ (CH₂)₂S(O)₂CH₂CF₂H CH₂SCH₂CF₂H CH(Me)S(O)(CH₂)₂CF₃ (CH₂)₂SCH₂CF₃ CH₂S(O)CH₂CF₂H CH(Me)S(O)₂(CH₂)₂CF₃ (CH₂)₂S(O)CH₂CF₃ CH₂S(O)₂CH₂CF₂H CH(Me)S(CH₂)₂Cl (CH₂)₂S(O)₂CH₂CF₃ CH₂SCH₂CF₃ CH(Me)S(O)(CH₂)₂Cl (CH₂)₂S(CH₂)₂Cl CH₂S(O)CH₂CF₃ CH(Me)S(O)₂(CH₂)₂Cl (CH₂)₂S(O)(CH₂)₂Cl CH₂S(O)₂CH₂CF₃ CH(Me)S(CH₂)₂Br (CH₂)₂S(O)₂(CH₂)₂Cl CH₂S(CH₂)₂CF₃ CH(Me)S(O)(CH₂)₂Br (CH₂)₂S(CH₂)₂Br CH₂S(O)(CH₂)₂CF₃ CH(Me)S(O)₂(CH₂)₂Br (CH₂)₂S(O)(CH₂)₂Br CH₂S(O)₂(CH₂)₂CF₃ C(Me)₂SCF₂H (CH₂)₂S(O)₂(CH₂)₂Br CH₂S(CH₂)₂Cl C(Me)₂S(O)CF₂H CH═CH₂ CH₂S(O)(CH₂)₂Cl C(Me)₂S(O)₂CF₂H CH═CHMe CH₂S(O)₂(CH₂)₂Cl C(Me)₂SCF₃ CH═CMe₂ CH₂S(CH₂)₂Br C(Me)₂S(O)CF₃ CH₂CH═CH₂ CH₂S(O)(CH₂)₂Br C(Me)₂S(O)₂CF₃ CH₂CH═CHMe CH₂S(O)₂(CH₂)₂Br C(Me)₂SCH₂CF₂H CH₂C(Me)═CH₂ CH₂SCHFCH₃ C(Me)₂S(O)CH₂CF₂H (CH₂)₂CH═CMe₂ CH₂SCF₂CH₃ C(Me)₂S(O)₂CH₂CF₂H C(Me)═CH₂ CH₂SCF(CH₃)₂ C(Me)₂SCH₂CF₃ C(Me)═CHMe CH₂SCF₂CF₂H C(Me)₂S(O)CH₂CF₃ C(Me)═CMe₂ CH₂SCF₂CF₃ C(Me)₂S(O)₂CH₂CF₃ CH(Me)CH═CH₂ CH₂SCF₂CF₂CF₃ C(Me)₂S(CH₂)₂CF₃ C(Et)═CH₂

TABLE 7 R^(1a) R^(1a) R^(1a) C(Et)═CHMe 2,4-(Cl)₂—Ph 3-F-4-Cl—Ph C(Et)═CMe₂ 2,5-(Cl)₂—Ph 3-F-5-Cl—Ph CH(Et)CH═CH₂ 2,6-(Cl)₂—Ph 2-Me-3-F—Ph C≡CH 3,4-(Cl)₂—Ph 2-Me-4-F—Ph C≡CMe 3,5-(Cl)₂—Ph 2-Me-5-F—Ph CH₂C≡CH 2,3-(Me)₂—Ph 3-Me-4-F—Ph CH₂C≡CMe 2,4-(Me)₂—Ph 3-Me-5-F—Ph CH(Me)C≡CH 2,5-(Me)₂—Ph 2-Cl-3-MeO—Ph CH(Me)C≡CMe 2,6-(Me)₂—Ph 2-Cl-4-MeO—Ph Ph 3,4-(Me)₂—Ph 2-Cl-5-MeO—Ph 2-F—Ph 3,5-(Me)₂—Ph 2-Cl-6-MeO—Ph 3-F—Ph 2,3-(MeO)₂—Ph 3-Cl-4-MeO—Ph 4-F—Ph 2,4-(MeO)₂—Ph 3-Cl-5-MeO—Ph 2-Cl—Ph 2,5-(MeO)₂—Ph 2-F-3-MeO—Ph 3-Cl—Ph 2,6-(MeO)₂—Ph 2-F-4-MeO—Ph 4-Cl—Ph 3,4-(MeO)₂—Ph 2-F-5-MeO—Ph 2-Br—Ph 3,5-(MeO)₂—Ph 2-F-6-MeO—Ph 3-Br—Ph 2-Cl-3-Me—Ph 3-F-4-MeO—Ph 4-Br—Ph 2-Cl-4-Me—Ph 3-F-5-MeO—Ph 2-Me—Ph 2-Cl-5-Me—Ph 2-MeO-3-F—Ph 3-Me—Ph 3-Cl-4-Me—Ph 2-MeO-4-F—Ph 4-Me—Ph 3-Cl-5-Me—Ph 2-MeO-5-F—Ph 2-CF₃—Ph 2-Cl-3-F—Ph 2-MeO-6-F—Ph 3-CF₃—Ph 2-Cl-4-F—Ph 3-MeO-4-F—Ph 4-CF₃—Ph 2-Cl-5-F—Ph 3-MeO-5-F—Ph 2-MeO—Ph 3-Cl-4-F—Ph 2-MeO-3-Cl—Ph 3-MeO—Ph 3-Cl-5-F—Ph 2-MeO-4-Cl—Ph 4-MeO—Ph 2-F-3-Me—Ph 2-MeO-5-Cl—Ph 2,3-(F)₂—Ph 2-F-4-Me—Ph 2-MeO-6-Cl—Ph 2,4-(F)₂—Ph 2-F-5-Me—Ph 3-MeO-4-Cl—Ph 2,5-(F)₂—Ph 3-F-4-Me—Ph 3-MeO-5-Cl—Ph 2,6-(F)₂—Ph 3-F-5-Me—Ph 2-Me-3-MeO—Ph 3,4-(F)₂—Ph 2-F-3-Cl—Ph 2-Me-4-MeO—Ph 3,5-(F)₂—Ph 2-F-4-Cl—Ph 2-Me-5-MeO—Ph 2,3-(Cl)₂—Ph 2-F-5-Cl—Ph 2-Me-6-MeO—Ph

TABLE 8 R^(1a) R^(1a) R^(1a) 3-Me-4-MeO—Ph D-11 CH₂(2,5-(MeO)₂—Ph) 3-Me-5-MeO—Ph D-12 CH₂(2,6-(MeO)₂—Ph) 2-MeO-3-Me—Ph D-13a CH₂(3,4-(MeO)₂—Ph) 2-MeO-4-Me—Ph D-14 CH₂(3,5-(MeO)₂—Ph) 2-MeO-5-Me—Ph D-16 CH(Me)(2-MeO—Ph) 2-MeO-6-Me—Ph D-16a CH(Me)(3-MeO—Ph) 3-MeO-4-Me—Ph D-16b CH(Me)(4-MeO—Ph) 3-MeO-5-Me—Ph D-16c CH(Me)(2,3-(MeO)₂—Ph) 3,5-(F)₂-4-Me—Ph D-16d CH(Me)(2,4-(MeO)₂—Ph) 3,5-(F)₂-4-MeO—Ph D-16e CH(Me)(2,5-(MeO)₂—Ph) 3,4,5-(MeO)₃—Ph D-16f CH(Me)(2,6-(MeO)₂—Ph) D-3 D-16g CH(Me)(3,4-(MeO)₂—Ph) D-3a D-16h CH(Me)(3,5-(MeO)₂—Ph) D-4 D-16i CH(Et)(2-MeO—Ph) D-4a D-16j CH(Et)(3-MeO—Ph) D-4b D-16k CH(Et)(4-MeO—Ph) D-8 D-16m (CH₂)₂(2-MeO—Ph) D-8a D-16n (CH₂)₂(3-MeO—Ph) D-8b D-16p (CH₂)₂(4-MeO—Ph) D-8c D-17 CHO D-8d D-17a CH═NOMe D-8e D-17b OMe D-8f D-19 OEt D-8g D-24a OPr-n D-8h D-24b OPr-i D-9 D-24c OBu-n D-9a D-24d OBu-i D-9c D-24e OBu-s D-9d D-24f OBu-t D-9f CH₂Ph OPen-n D-9g CH₂(2-MeO—Ph) OPen-i D-9i CH₂(3-MeO—Ph) OPen-s D-9j CH₂(4-MeO—Ph) OPen-t D-9m CH₂(2,3-(MeO)₂—Ph) OHex-n D-10a CH₂(2,4-(MeO)₂—Ph) SMe

TABLE 9 R^(1a) R^(1a) R^(1a) S(O)Me SPen-n S(CH₂)₂Cl S(O)₂Me S(O)Pen-n S(O)(CH₂)₂Cl SEt S(O)₂Pen-n S(O)₂(CH₂)₂Cl S(O)Et SPen-i SCH(Me)CH₂Cl S(O)₂Et S(O)Pen-i SCH₂CH(Me)Cl SPr-n S(O)₂Pen-i S(CH₂)₃Cl S(O)Pr-n SPen-c SCF₃ S(O)₂Pr-n S(O)Pen-c SCH₂CF₃ SPr-i S(O)₂Pen-c S(O)CH₂CF₃ S(O)Pr-i SPen-s S(O)₂CH₂CF₃ S(O)₂Pr-i S(O)Pen-s SCH(Me)CF₃ SPr-c S(O)₂Pen-s S(CH₂)₂CF₃ S(O)Pr-c SPen-t S(CH₂)₃CF₃ S(O)₂Pr-c S(O)Pen-t SCHFCH₃ S(D-16) S(O)₂Pen-t SCF₂CH₃ S(O)(D-16) SHex-n SCF(CH₃)₂ S(O)₂(D-16) SHex-c SCF₂CF₂H S(D-16e) SCH₂CH═CH₂ SCF₂CF₃ S(O)(D-16e) S(O)CH₂CH═CH₂ SCF₂CF₂CF₃ S(O)₂(D-16e) S(O)₂CH₂CH═CH₂ SCF(CF₃) SBu-n SCH(Me)CH═CH₂ SCH₂OMe S(O)Bu-n SC(Me)₂CH═CH₂ S(CH₂)₂OMe S(O)₂Bu-n SCH₂CH═CHMe S(O)(CH₂)₂OMe SBu-i SCH₂C(Me)═CH₂ S(O)₂(CH₂)₂OMe S(O)Bu-i S(CH₂)₂CH═CMe₂ SCH(Me)CH₂OMe S(O)₂Bu-i SC(Me)═CH₂ S(O)CH(Me)CH₂OMe SBu-c SC(Me)═CH(Me) S(O)₂CH(Me)CH₂OMe S(O)Bu-c SCH₂C≡CH SCH₂CH(Me)OMe S(O)₂Bu-c S(O)CH₂C≡CH S(O)CH₂CH(Me)OMe SBu-s S(O)₂CH₂C≡CH S(O)₂CH₂CH(Me)OMe S(O)Bu-s SCH(Me)C≡CH SC(Me)₂CH₂OMe S(O)₂Bu-s SC(Me)₂C≡CH S(CH₂)₃OMe SBu-t SCH₂C≡CMe SCH₂OEt S(O)Bu-t SCH₂Cl S(CH₂)₂OEt S(O)₂Bu-t SCH(Me)Cl S(O)(CH₂)₂OEt

TABLE 10 R^(1a) R^(1a) R^(1a) S(O)₂(CH₂)₂OEt S(O)₂CH₂CN SCH(Me)C(O)Me SCH(Me)CH₂OEt SCH(Me)CN S(CH₂)₂C(O)Me SCH₂OPr-i S(O)CH(Me)CN SCH₂C(O)OMe S(CH₂)₂OPr-i S(O)₂CH(Me)CN SCH(Me)C(O)OMe S(O)(CH₂)₂OPr-i SC(Me)₂CN S(CH₂)₂C(O)OMe S(O)₂(CH₂)₂OPr-i S(O)C(Me)₂CN SCH₂C(O)OEt SCH(Me)CH₂OPr-i S(O)₂C(Me)₂CN SCH(Me)C(O)OEt SCH₂Pr-c S(CH₂)₂CN S(CH₂)₂C(O)OEt S(O)CH₂Pr-c S(O)(CH₂)₂CN SCH₂(D-8a) S(O)₂CH₂Pr-c S(O)₂(CH₂)₂CN S(O)CH₂(D-8a) SCH(Me)Pr-c SCH₂Ph S(O)₂CH₂(D-8a) S(O)CH(Me)Pr-c S(O)CH₂Ph SCH₂(D-8b) S(O)₂CH(Me)Pr-c S(O)₂CH₂Ph S(O)CH₂(D-8b) S(CH₂)₂Pr-c SCH(Me)Ph S(O)₂CH₂(D-8b) SCH₂(D-16) S(O)CH(Me)Ph SCH₂(D-8c) S(O)CH₂(D-16) S(O)₂CH(Me)Ph S(O)CH₂(D-8c) S(O)₂CH₂(D-16) SCH₂(2-MeO—Ph) S(O)₂CH₂(D-8c) SCH₂(D-16e) S(O)CH₂(2-MeO—Ph) SCH₂(D-8d) S(O)CH₂(D-16e) S(O)₂CH₂(2-MeO—Ph) S(O)CH₂(D-8d) S(O)₂CH₂(D-16e) SCH(Me)(2-MeO—Ph) S(O)₂CH₂(D-8d) SCH₂Bu-c S(O)CH(Me)(2-MeO—Ph) SCH₂(D-8e) S(O)CH₂Bu-c S(O)₂CH(Me)(2-MeO—Ph) S(O)₂CH₂(D-8e) S(O)₂CH₂Bu-c SCH₂(3-MeO—Ph) SCH₂(D-8f) SCH(Me)Bu-c S(O)CH₂(3-MeO—Ph) S(O)₂CH₂(D-8f) S(CH₂)₂Bu-c S(O)₂CH₂(3-MeO—Ph) SCH₂(D-8g) SCH₂Pen-c SCH(Me)(3-MeO—Ph) S(O)₂CH₂(D-8g) S(O)CH₂Pen-c S(O)CH(Me)(3-MeO—Ph) SCH₂(D-8h) S(O)₂CH₂Pen-c S(O)₂CH(Me)(3-MeO—Ph) S(O)₂CH₂(D-8h) SCH(Me)Pen-c SCH₂(4-MeO—Ph) SCH₂(D-15) S(CH₂)₂Pen-c S(O)CH₂(4-MeO—Ph) S(O)CH₂(D-15) SCH₂Hex-c S(O)₂CH₂(4-MeO—Ph) S(O)₂CH₂(D-15) SCH(Me)Hex-c SCH(Me)(4-MeO—Ph) SCH(Me)(D-15) S(CH₂)₂Hex-c S(O)CH(Me)(4-MeO—Ph) S(O)CH(Me)(D-15) SCH₂CN S(O)₂CH(Me)(4-MeO—Ph) S(O)₂CH(Me)(D-15) S(O)CH₂CN SCH₂C(O)Me S(CH₂)₂(D-15)

TABLE 11 R^(1a) R^(1a) R^(1a) S(O)(CH₂)₂(D-15) N(Me)Pr-c N(Pr-i)Pr-i S(O)₂(CH₂)₂(D-15) N(Me)(D-16) N(Pr-i)Pr-c SCH₂(D-18) N(Me)(D-16e) N(Pr-i)(D-16) S(O)CH₂(D-18) N(Me)Bu-n N(Pr-i)(D-16e) S(O)₂CH₂(D-18) N(Me)Bu-i N(Pr-i)Bu-n SCH(Me)(D-18) N(Me)Bu-c N(Pr-i)Bu-i S(O)CH(Me)(D-18) N(Me)Bu-s N(Pr-i)Bu-c S(O)₂CH(Me)(D-18) N(Me)Bu-t N(Pr-i)Bu-s S(CH₂)₂(D-18) N(Me)Pen-n NHCH₂OMe S(O)(CH₂)₂(D-18) N(Me)Pen-i NHCH₂OEt S(O)₂(CH₂)₂(D-18) N(Me)Pen-c NHCH(Me)OMe NHMe N(Me)Pen-s NHCH(Me)OEt NHEt N(Me)Pen-t NHC(Me)₂OMe NHPr-n N(Me)(3-Pen) NHC(Me)₂OEt NHPr-i N(Me)Hex-n NH(CH₂)₂OMe NHPr-c N(Me)Hex-c NH(CH₂)₂OEt NH(D-16) N(Et)Et NH(CH₂)₂OPr-n NH(D-16e) N(Et)Pr-n NH(CH₂)₂OPr-i NHBu-n N(Et)Pr-i N(Me)CH₂OMe NHBu-i N(Et)Pr-c N(Me)CH₂OEt NHBu-c N(Et)(D-16) N(Me)CH(Me)OMe NHBu-s N(Et)(D-16e) N(Me)CH(Me)OEt NHBu-t N(Et)Bu-n N(Me)C(Me)₂OMe NHPen-n N(Et)Bu-i N(Me)C(Me)₂OEt NHPen-i N(Et)Bu-c N(Me)(CH₂)₂OMe NHPen-c N(Et)Bu-s N(Me)(CH₂)₂OEt NHPen-s N(Pr-n)Pr-n N(Me)(CH₂)₂OPr-n NHPen-t N(Pr-n)Pr-i N(Me)(CH₂)₂OPr-i NH(3-Pen) N(Pr-n)Pr-c N(Et)C(Me)₂OMe NHHex-n N(Pr-n)(D-16) N(Et)C(Me)₂OEt NHHex-c N(Pr-n)(D-16e) N(Et)(CH₂)₂OMe N(Me)Me N(Pr-n)Bu-n N(Et)(CH₂)₂OEt N(Me)Et N(Pr-n)Bu-i N(Et)(CH₂)₂OPr-n N(Me)Pr-n N(Pr-n)Bu-c N(Et)(CH₂)₂OPr-i N(Me)Pr-i N(Pr-n)Bu-s N(Pr-n)(CH₂)₂OMe

TABLE 12 R^(1a) R^(1a) R^(1a) N(Pr-n)(CH₂)₂OEt N(Me)(CH₂)₂S(O)Pr-i NH(2,6-(MeO)₂—Ph) N(Pr-n)(CH₂)₂OPr-n N(Me)(CH₂)₂S(O)₂Pr-i NH(3,4-(MeO)₂—Ph) N(Pr-n)(CH₂)₂OPr-i NHCF₂H NH(3,5-(MeO)₂—Ph) N(Pr-i)(CH₂)₂OMe NHCF₃ N(Me)Ph N(Pr-i)(CH₂)₂OEt NHCH₂CF₂H N(Me)(2-MeO—Ph) N(Pr-i)(CH₂)₂OPr-n NHCH₂CF₃ N(Me)(3-MeO—Ph) N(Pr-i)(CH₂)₂OPr-i NH(CH₂)₂CF₃ N(Me)(4-MeO—Ph) NHCH₂SMe NH(CH₂)₂Cl N(Me)(2,3-(MeO)₂—Ph) NHCH₂SEt NH(CH₂)₃Cl N(Me)(2,4-(MeO)₂—Ph) NHCH(Me)SMe N(Me)CF₂H N(Me)(2,5-(MeO)₂—Ph) NHCH(Me)SEt N(Me)CF₃ N(Me)(2,6-(MeO)₂—Ph) NHC(Me)₂SMe N(Me)CH₂CF₂H N(Me)(3,4-(MeO)₂—Ph) NHC(Me)₂SEt N(Me)CH₂CF₃ N(Me)(3,5-(MeO)₂—Ph) NH(CH₂)₂SMe N(Me)(CH₂)₂CF₃ NHCH₂Ph NH(CH₂)₂S(O)Me N(Me)(CH₂)₂Cl NHCH₂(2-MeO—Ph) NH(CH₂)₂S(O)₂Me N(Me)(CH₂)₃Cl NHCH₂(3-MeO—Ph) NH(CH₂)₂SEt NHCH₂CH═CH₂ NHCH₂(4-MeO—Ph) NH(CH₂)₂S(O)Et N(Me)CH₂CH═CH₂ N(Me)CH₂Ph NH(CH₂)₂S(O)₂Et NHCH₂C≡CH N(Me)CH₂(2-MeO—Ph) NH(CH₂)₂SPr-i NHCH₂C≡CMe N(Me)CH₂(3-MeO—Ph) NH(CH₂)₂S(O)Pr-i N(Me)CH₂C≡CH N(Me)CH₂(4-MeO—Ph) NH(CH₂)₂S(O)₂Pr-i N(Me)CH₂C≡CMe NH(D-9b) N(Me)CH₂SMe NHCH₂CN NH(D-9e) N(Me)CH₂SEt NH(CH₂)₂CN NH(D-9h) N(Me)CH(Me)SMe NH(CH₂)₃CN NH(D-9k) N(Me)CH(Me)SEt N(Me)CH₂CN N(Me)(D-9b) N(Me)C(Me)₂SMe N(Me)(CH₂)₂CN N(Me)(D-9e) N(Me)C(Me)₂SEt N(Me)(CH₂)₃CN N(Me)(D-9h) N(Me)(CH₂)₂SMe NHPh N(Me)(D-9k) N(Me)(CH₂)₂S(O)Me NH(2-MeO—Ph) NHSO₂Ph N(Me)(CH₂)₂S(O)₂Me NH(3-MeO—Ph) N(Me)SO₂Ph N(Me)(CH₂)₂SEt NH(4-MeO—Ph) N(Me)(CH₂)₂S(O)Et NH(2,3-(MeO)₂—Ph) N(Me)(CH₂)₂S(O)₂Et NH(2,4-(MeO)₂—Ph) N(Me)(CH₂)₂SPr-i NH(2,5-(MeO)₂—Ph)

SECOND TABLE

TABLE 13 R^(1a) R^(1a) R^(1a) H CH₂OHex-n C(Me)₂OMe F CH(Me)OMe C(Me)₂OEt Cl CH(Me)OEt C(Me)₂OPr-n Br CH(Me)OPr-n C(Me)₂OPr-i I CH(Me)OPr-i C(Me)₂OBu-n Me CH(Me)OBu-n C(Me)₂OBu-i Et CH(Me)OBu-i C(Me)₂OBu-s Pr-n CH(Me)OBu-s C(Me)₂OBu-t Pr-i CH(Me)OBu-t (CH₂)₂OMe Pr-c CH(Me)OPen-n (CH₂)₂OEt Bu-n CH(Me)OPen-i (CH₂)₂OPr-n Bu-i CH(Me)OPen-s (CH₂)₂OPr-i Bu-c CH(Me)OPen-t (CH₂)₂OBu-n Bu-s CH(Me)OHex-n (CH₂)₂OBu-i Bu-t CH(Et)OMe (CH₂)₂OBu-s Pen-n CH(Et)OEt (CH₂)₂OBu-t Pen-i CH(Et)OPr-n CH(Me)CH₂OMe Pen-c CH(Et)OPr-i CH(Me)CH₂OEt Pen-s CH(Et)OBu-n CH(Me)CH₂OPr-n Pen-t CH(Et)OBu-i CH(Me)CH₂OPr-i 3-Pen CH(Et)OBu-s CH(Me)CH₂OBu-n Hex-n CH(Et)OBu-t CH(Me)CH₂OBu-i Hex-c CH(Et)OPen-n CH(Me)CH₂OBu-s CH₂OMe CH(Et)OPen-i CH(Me)CH₂OBu-t CH₂OEt CH(Et)OPen-s CH(Et)CH₂OMe CH₂OPr-n CH(Et)OPen-t CH(Et)CH₂OEt CH₂OPr-i CH(Et)OHex-n (CH₂)₃OMe CH₂OBu-n CH(Pr-n)OMe (CH₂)₃OEt CH₂OBu-i CH(Pr-n)OEt (CH₂)₃OPr-n CH₂OBu-s CH(Pr-n)OPr-n (CH₂)₃OPr-i CH₂OBu-t CH(Pr-n)OPr-i (CH₂)₃OBu-n CH₂OPen-n CH(Pr-i)OMe (CH₂)₃OBu-i CH₂OPen-i CH(Pr-i)OEt (CH₂)₃OBu-s CH₂OPen-s CH(Pr-i)OPr-n (CH₂)₃OBu-t CH₂OPen-t CH(Pr-i)OPr-i CH₂OCF₂H

TABLE 14 R^(1a) R^(1a) R^(1a) CH₂OCF₃ CH(iPr)OH C(Me)₂OCH₂OPr-n CH₂OCH₂CF₂H C(Me)₂OH C(Me)₂OCH₂OPr-i CH₂OCH₂CF₃ (CH₂)₂OH C(Me)₂O(CH₂)₂OMe CH₂O(CH₂)₂CF₃ CH(Me)CH₂OH C(Me)₂O(CH₂)₂OEt CH₂O(CH₂)₂Cl (CH₂)₃OH C(Me)₂O(CH₂)₂OPr-n CH₂O(CH₂)₂Br CH₂OCH₂OMe C(Me)₂O(CH₂)₂OPr-i CH(Me)OCF₂H CH₂OCH₂OEt (CH₂)₂OCH₂OMe CH(Me)OCF₃ CH₂OCH₂OPr-n (CH₂)₂OCH₂OEt CH(Me)OCH₂CF₂H CH₂OCH₂OPr-i (CH₂)₂OCH₂OPr-n CH(Me)OCH₂CF₃ CH₂O(CH₂)₂OMe (CH₂)₂OCH₂OPr-i CH(Me)O(CH₂)₂CF₃ CH₂O(CH₂)₂OEt (CH₂)₂O(CH₂)₂OMe CH(Me)O(CH₂)₂Cl CH₂O(CH₂)₂OPr-n (CH₂)₂O(CH₂)₂OEt CH(Me)O(CH₂)₂Br CH₂O(CH₂)₂OPr-i (CH₂)₂O(CH₂)₂OPr-n CH(Et)OCF₂H CH₂OCH(Me)CH₂OMe (CH₂)₂O(CH₂)₂OPr-i CH(Et)OCF₃ CH₂OCH(Me)CH₂OEt CH(Me)CH₂OCH₂OMe CH(Et)OCH₂CF₂H CH₂OCH₂CH(Me)OMe CH(Me)CH₂OCH₂OEt CH(Et)OCH₂CF₃ CH₂OCH₂CH(Me)OEt CH(Me)CH₂O(CH₂)₂OMe CH(Et)O(CH₂)₂CF₃ CH₂OCH(Me)OMe CH(Me)CH₂O(CH₂)₂OEt CH(Et)O(CH₂)₂Cl CH₂OCH(Me)OEt CH(Et)CH₂OCH₂OMe CH(Et)O(CH₂)₂Br CH₂O(CH₂)₃OMe CH(Et)CH₂OCH₂OEt C(Me)₂OCF₂H CH₂O(CH₂)₃OEt CH(Et)CH₂O(CH₂)₂OMe C(Me)₂OCF₃ CH(Me)OCH₂OMe CH(Et)CH₂O(CH₂)₂OEt C(Me)₂OCH₂CF₂H CH(Me)OCH₂OEt CH(Et)O(CH₂)₂OMe C(Me)₂OCH₂CF₃ CH(Me)OCH₂OPr-n CH(Et)O(CH₂)₂OEt C(Me)₂O(CH₂)₂CF₃ CH(Me)OCH₂OPr-i CH(Et)O(CH₂)₂OPr-n C(Me)₂O(CH₂)₂Cl CH(Me)O(CH₂)₂OMe CH(Et)O(CH₂)₂OPr-i C(Me)₂O(CH₂)₂Br CH(Me)O(CH₂)₂OEt CH(Pr-n)O(CH₂)₂OMe (CH₂)₂OCF₃ CH(Me)O(CH₂)₂OPr-n CH(Pr-n)O(CH₂)₂OEt (CH₂)₂OCH₂CF₂H CH(Me)O(CH₂)₂OPr-i CH(Pr-n)O(CH₂)₂OPr-n (CH₂)₂OCH₂CF₃ CH(Me)OCH(Me)CH₂OMe CH(Pr-n)O(CH₂)₂OPr-i (CH₂)₂O(CH₂)₂Cl CH(Me)OCH(Me)CH₂OEt CH(Pr-i)O(CH₂)₂OMe (CH₂)₂O(CH₂)₂Br CH(Me)OCH₂CH(Me)OMe CH(Pr-i)O(CH₂)₂OEt CH₂OH CH(Me)OCH₂CH(Me)OEt CH(Pr-i)O(CH₂)₂OPr-n CH(Me)OH C(Me)₂OCH₂OMe CH(Pr-i)O(CH₂)₂OPr-i CH(Et)OH C(Me)₂OCH₂OEt CH₂OC(O)Me

TABLE 15 R^(1a) R^(1a) R^(1a) CH₂OC(O)Et CH(Et)C(O)OEt CH₂S(O)Pen-n CH₂OC(O)Pr-i CH(Et)C(O)OPr-i CH₂S(O)₂Pen-n CH(Me)OC(O)Me CH(Et)C(O)OCH₂OMe CH₂SPen-i CH(Me)OC(O)Et CH(Et)C(O)O(CH₂)₂OMe CH₂S(O)Pen-i CH(Me)OC(O)Pr-i CH(Et)C(O)O(CH₂)₂OEt CH₂S(O)₂Pen-i CH(Et)OC(O)Me CH(Et)C(O)O(CH₂)₂OPr-i CH₂SPen-s CH(Et)OC(O)Et (CH₂)₂C(O)OMe CH₂S(O)Pen-s CH(Et)OC(O)Pr-i (CH₂)₂C(O)OEt CH₂S(O)₂Pen-s CH₂OPh (CH₂)₂C(O)O(CH₂)₂OMe CH₂SPen-t CH(Me)OPh (CH₂)₂C(O)O(CH₂)₂OEt CH₂S(O)Pen-t CH₂C(O)OMe CH₂SMe CH₂S(O)₂Pen-t CH₂C(O)OEt CH₂S(O)Me CH₂SHex-n CH₂C(O)OPr-n CH₂S(O)₂Me CH(Me)SMe CH₂C(O)OPr-i CH₂SEt CH(Me)S(O)Me CH₂C(O)OBu-n CH₂S(O)Et CH(Me)S(O)₂Me CH₂C(O)OBu-i CH₂S(O)₂Et CH(Me)SEt CH₂C(O)OBu-s CH₂SPr-n CH(Me)S(O)Et CH₂C(O)OBu-t CH₂S(O)Pr-n CH(Me)S(O)₂Et CH₂C(O)OPen-n CH₂S(O)₂Pr-n CH(Me)SPr-n CH₂C(O)OPen-i CH₂SPr-i CH(Me)S(O)Pr-n CH₂C(O)OPen-s CH₂S(O)Pr-i CH(Me)S(O)₂Pr-n CH₂C(O)OPen-t CH₂S(O)₂Pr-i CH(Me)SPr-i CH₂C(O)OHex-n CH₂SBu-n CH(Me)S(O)Pr-i CH₂C(O)OCH₂OMe CH₂S(O)Bu-n CH(Me)S(O)₂Pr-i CH₂C(O)O(CH₂)₂OMe CH₂S(O)₂Bu-n CH(Me)SBu-n CH₂C(O)O(CH₂)₂OEt CH₂SBu-i CH(Me)S(O)Bu-n CH₂C(O)O(CH₂)₂OPr-i CH₂S(O)Bu-i CH(Me)S(O)₂Bu-n CH(Me)C(O)OMe CH₂S(O)₂Bu-i CH(Me)SBu-i CH(Me)C(O)OEt CH₂SBu-s CH(Me)S(O)Bu-i CH(Me)C(O)OPr-i CH₂S(O)Bu-s CH(Me)S(O)₂Bu-i CH(Me)C(O)OCH₂OMe CH₂S(O)₂Bu-s CH(Me)SBu-s CH(Me)C(O)O(CH₂)₂OMe CH₂SBu-t CH(Me)S(O)Bu-s CH(Me)C(O)O(CH₂)₂OEt CH₂S(O)Bu-t CH(Me)S(O)₂Bu-s CH(Me)C(O)O(CH₂)₂OPr-i CH₂S(O)₂Bu-t CH(Me)SBu-t CH(Et)C(O)OMe CH₂SPen-n CH(Me)S(O)Bu-t

TABLE 16 R^(1a) R^(1a) R^(1a) CH(Me)S(O)₂Bu-t C(Me)₂SBu-t CH(Me)CH₂S(O)₂Me CH(Me)SPen-n C(Me)₂S(O)Bu-t CH(Me)CH₂SEt CH(Me)S(O)Pen-n C(Me)₂S(O)₂Bu-t CH(Me)CH₂S(O)Et CH(Me)S(O)₂Pen-n C(Me)₂SPen-n CH(Me)CH₂S(O)₂Et CH(Me)SPen-i C(Me)₂S(O)Pen-n CH(Me)CH₂SPr-n CH(Me)S(O)Pen-i C(Me)₂S(O)₂Pen-n CH(Me)CH₂S(O)Pr-n CH(Me)S(O)₂Pen-i C(Me)₂SPen-i CH(Me)CH₂S(O)₂Pr-n CH(Me)SPen-s C(Me)₂S(O)Pen-i CH(Me)CH₂SPr-i CH(Me)S(O)Pen-s C(Me)₂S(O)₂Pen-i CH(Me)CH₂S(O)Pr-i CH(Me)S(O)₂Pen-s C(Me)₂SPen-s CH(Me)CH₂S(O)₂Pr-i CH(Me)SPen-t C(Me)₂S(O)Pen-s CH(Et)CH₂SMe CH(Me)S(O)Pen-t C(Me)₂S(O)₂Pen-s CH(Et)CH₂S(O)Me CH(Me)S(O)₂Pen-t C(Me)₂SPen-t CH(Et)CH₂S(O)₂Me CH(Me)SHex-n C(Me)₂S(O)Pen-t CH(Et)CH₂SEt C(Me)₂SMe C(Me)₂S(O)₂Pen-t CH(Et)CH₂S(O)Et C(Me)₂S(O)Me (CH₂)₂SMe CH(Et)CH₂S(O)₂Et C(Me)₂S(O)₂Me (CH₂)₂S(O)Me C(Me)₂CH₂SMe C(Me)₂SEt (CH₂)₂S(O)₂Me C(Me)₂CH₂S(O)Me C(Me)₂S(O)Et (CH₂)₂SEt C(Me)₂CH₂S(O)₂Me C(Me)₂S(O)₂Et (CH₂)₂S(O)Et C(Me)₂CH₂SEt C(Me)₂SPr-n (CH₂)₂S(O)₂Et C(Me)₂CH₂S(O)Et C(Me)₂S(O)Pr-n (CH₂)₂SPr-n C(Me)₂CH₂S(O)₂Et C(Me)₂S(O)₂Pr-n (CH₂)₂S(O)Pr-n C(Me)₂CH₂SPr-n C(Me)₂SPr-i (CH₂)₂S(O)₂Pr-n C(Me)₂CH₂S(O)Pr-n C(Me)₂S(O)Pr-i (CH₂)₂SPr-i C(Me)₂CH₂S(O)₂Pr-n C(Me)₂S(O)₂Pr-i (CH₂)₂S(O)Pr-i C(Me)₂CH₂SPr-i C(Me)₂SBu-n (CH₂)₂S(O)₂Pr-i C(Me)₂CH₂S(O)Pr-i C(Me)₂S(O)Bu-n (CH₂)₃SMe C(Me)₂CH₂S(O)₂Pr-i C(Me)₂S(O)₂Bu-n (CH₂)₃S(O)Me CH(Et)SMe C(Me)₂SBu-i (CH₂)₃S(O)₂Me CH(Et)S(O)Me C(Me)₂S(O)Bu-i (CH₂)₃SEt CH(Et)S(O)₂Me C(Me)₂S(O)₂Bu-i (CH₂)₃S(O)Et CH(Et)SEt C(Me)₂SBu-s (CH₂)₃S(O)₂Et CH(Et)S(O)Et C(Me)₂S(O)Bu-s CH(Me)CH₂SMe CH(Et)S(O)₂Et C(Me)₂S(O)₂Bu-s CH(Me)CH₂S(O)Me CH(Et)SPr-n

TABLE 17 R^(1a) R^(1a) R^(1a) CH(Et)S(O)Pr-n CH₂SCH₂CF₂H CH(Me)S(O)(CH₂)₂CF₃ CH(Et)S(O)₂Pr-n CH₂S(O)CH₂CF₂H CH(Me)S(O)₂(CH₂)₂CF₃ CH(Et)SPr-i CH₂S(O)₂CH₂CF₂H CH(Me)S(CH₂)₂Cl CH(Et)S(O)Pr-i CH₂SCH₂CF₃ CH(Me)S(O)(CH₂)₂Cl CH(Et)S(O)₂Pr-i CH₂S(O)CH₂CF₃ CH(Me)S(O)₂(CH₂)₂Cl CH(Pr-n)SMe CH₂S(O)₂CH₂CF₃ CH(Me)S(CH₂)₂Br CH(Pr-n)S(O)Me CH₂S(CH₂)₂CF₃ CH(Me)S(O)(CH₂)₂Br CH(Pr-n)S(O)₂Me CH₂S(O)(CH₂)₂CF₃ CH(Me)S(O)₂(CH₂)₂Br CH(Pr-n)SEt CH₂S(O)₂(CH₂)₂CF₃ C(Me)₂SCF₂H CH(Pr-n)S(O)Et CH₂S(CH₂)₂Cl C(Me)₂S(O)CF₂H CH(Pr-n)S(O)₂Et CH₂S(O)(CH₂)₂Cl C(Me)₂S(O)₂CF₂H CH(Pr-n)SPr-n CH₂S(O)₂(CH₂)₂Cl C(Me)₂SCF₃ CH(Pr-n)S(O)Pr-n CH₂S(CH₂)₂Br C(Me)₂S(O)CF₃ CH(Pr-n)S(O)₂Pr-n CH₂S(O)(CH₂)₂Br C(Me)₂S(O)₂CF₃ CH(Pr-n)SPr-i CH₂S(O)₂(CH₂)₂Br C(Me)₂SCH₂CF₂H CH(Pr-n)S(O)Pr-i CH₂SCHFCH₃ C(Me)₂S(O)CH₂CF₂H CH(Pr-n)S(O)₂Pr-i CH₂SCF₂CH₃ C(Me)₂S(O)₂CH₂CF₂H CH(Pr-i)SMe CH₂SCF(CH₃)₂ C(Me)₂SCH₂CF₃ CH(Pr-i)S(O)Me CH₂SCF₂CF₂H C(Me)₂S(O)CH₂CF₃ CH(Pr-i)S(O)₂Me CH₂SCF₂CF₃ C(Me)₂S(O)₂CH₂CF₃ CH(Pr-i)SEt CH₂SCF₂CF₂CF₃ C(Me)₂S(CH₂)₂CF₃ CH(Pr-i)S(O)Et CH₂SCF(CF₃)₂ C(Me)₂S(O)(CH₂)₂CF₃ CH(Pr-i)S(O)₂Et CH(Me)SCF₂H C(Me)₂S(O)₂(CH₂)₂CF₃ CH(Pr-i)SPr-n CH(Me)S(O)CF₂H C(Me)₂S(CH₂)₂Cl CH(Pr-i)S(O)Pr-n CH(Me)S(O)₂CF₂H C(Me)₂S(O)(CH₂)₂Cl CH(Pr-i)S(O)₂Pr-n CH(Me)SCF₃ C(Me)₂S(O)₂(CH₂)₂Cl CH(Pr-i)SPr-i CH(Me)S(O)CF₃ C(Me)₂S(CH₂)₂Br CH(Pr-i)S(O)Pr-i CH(Me)S(O)₂CF₃ C(Me)₂S(O)(CH₂)₂Br CH(Pr-i)S(O)₂Pr-i CH(Me)SCH₂CF₂H C(Me)₂S(O)₂(CH₂)₂Br CH₂SCF₂H CH(Me)S(O)CH₂CF₂H (CH₂)₂SCF₃ CH₂S(O)CF₂H CH(Me)S(O)₂CH₂CF₂H (CH₂)₂S(O)CF₃ CH₂S(O)₂CF₂H CH(Me)SCH₂CF₃ (CH₂)₂S(O)₂CF₃ CH₂SCF₃ CH(Me)S(O)CH₂CF₃ (CH₂)₂SCH₂CF₂H CH₂S(O)CF₃ CH(Me)S(O)₂CH₂CF₃ (CH₂)₂S(O)CH₂CF₂H CH₂S(O)₂CF₃ CH(Me)S(CH₂)₂CF₃ (CH₂)₂S(O)₂CH₂CF₂H

TABLE 18 R^(1a) R^(1a) R^(1a) (CH₂)₂SCH₂CF₃ 3-Cl—Ph 2-Cl-3-Me—Ph (CH₂)₂S(O)CH₂CF₃ 4-Cl—Ph 2-Cl-4-Me—Ph (CH₂)₂S(O)₂CH₂CF₃ 2-Br—Ph 2-Cl-5-Me—Ph (CH₂)₂S(CH₂)₂Cl 3-Br—Ph 3-Cl-4-Me—Ph (CH₂)₂S(O)(CH₂)₂Cl 4-Br—Ph 3-Cl-5-Me—Ph (CH₂)₂S(O)₂(CH₂)₂Cl 2-Me—Ph 2-Cl-3-F—Ph (CH₂)₂S(CH₂)₂Br 3-Me—Ph 2-Cl-4-F—Ph (CH₂)₂S(O)(CH₂)₂Br 4-Me—Ph 2-Cl-5-F—Ph (CH₂)₂S(O)₂(CH₂)₂Br 2-MeO—Ph 3-Cl-4-F—Ph CH═CH₂ 3-MeO—Ph 3-Cl-5-F—Ph CH═CHMe 4-MeO—Ph 2-F-3-Me—Ph CH═CMe₂ 2,3-(F)₂—Ph 2-F-4-Me—Ph CH₂CH═CH₂ 2,4-(F)₂—Ph 2-F-5-Me—Ph CH₂CH═CHMe 2,5-(F)₂—Ph 3-F-4-Me—Ph CH₂C(Me)═CH₂ 2,6-(F)₂—Ph 3-F-5-Me—Ph (CH₂)₂CH═CMe₂ 3,4-(F)₂—Ph 2-F-3-Cl—Ph C(Me)═CH₂ 3,5-(F)₂—Ph 2-F-4-Cl—Ph C(Me)═CHMe 2,3-(Cl)₂—Ph 2-F-5-Cl—Ph C(Me)═CMe₂ 2,4-(Cl)₂—Ph 3-F-4-Cl—Ph CH(Me)CH═CH₂ 2,5-(Cl)₂—Ph 3-F-5-Cl—Ph C(Et)═CH₂ 2,6-(Cl)₂—Ph 2-Me-3-F—Ph C(Et)═CHMe 3,4-(Cl)₂—Ph 2-Me-4-F—Ph C(Et)═CMe₂ 3,5-(Cl)₂—Ph 2-Me-5-F—Ph CH(Et)CH═CH₂ 2,3-(Me)₂—Ph 3-Me-4-F—Ph C≡CH 2,4-(Me)₂—Ph 3-Me-5-F—Ph C≡CMe 2,5-(Me)₂—Ph 2-Cl-3-MeO—Ph CH₂C≡CH 2,6-(Me)₂—Ph 2-Cl-4-MeO—Ph CH₂C≡CMe 3,4-(Me)₂—Ph 2-Cl-5-MeO—Ph CH(Me)C≡CH 3,5-(Me)₂—Ph 2-Cl-6-MeO—Ph CH(Me)C≡CMe 2,3-(MeO)₂—Ph 3-Cl-4-MeO—Ph Ph 2,4-(MeO)₂—Ph 3-Cl-5-MeO—Ph 2-F—Ph 2,5-(MeO)₂—Ph 2-F-3-MeO—Ph 3-F—Ph 2,6-(MeO)₂—Ph 2-F-4-MeO—Ph 4-F—Ph 3,4-(MeO)₂—Ph 2-F-5-MeO—Ph 2-Cl—Ph 3,5-(MeO)₂—Ph 2-F-6-MeO—Ph

TABLE 19 R^(1a) R^(1a) R^(1a) 3-F-4-MeO—Ph D-8 CH₂(2,4-(MeO)₂—Ph) 3-F-5-MeO—Ph D-8a CH₂(2,5-(MeO)₂—Ph) 2-MeO-3-F—Ph D-8b CH₂(2,6-(MeO)₂—Ph) 2-MeO-4-F—Ph D-8c CH₂(3,4-(MeO)₂—Ph) 2-MeO-5-F—Ph D-8d CH₂(3,5-(MeO)₂—Ph) 2-MeO-6-F—Ph D-8e CH(Me)(2-MeO—Ph) 3-MeO-4-F—Ph D-8f CH(Me)(3-MeO—Ph) 3-MeO-5-F—Ph D-8g CH(Me)(4-MeO—Ph) 2-MeO-3-Cl—Ph D-8h CH(Me)(2,3-(MeO)₂—Ph) 2-MeO-4-Cl—Ph D-10a CH(Me)(2,4-(MeO)₂—Ph) 2-MeO-5-Cl—Ph D-11 CH(Me)(2,5-(MeO)₂—Ph) 2-MeO-6-Cl—Ph D-14 CH(Me)(2,6-(MeO)₂—Ph) 3-MeO-4-Cl—Ph D-16 CH(Me)(3,4-(MeO)₂—Ph) 3-MeO-5-Cl—Ph D-16a CH(Me)(3,5-(MeO)₂—Ph) 2-Me-3-MeO—Ph D-16b CH(Et)(2-MeO—Ph) 2-Me-4-MeO—Ph D-16c CH(Et)(3-MeO—Ph) 2-Me-5-MeO—Ph D-16d CH(Et)(4-MeO—Ph) 2-Me-6-MeO—Ph D-16e (CH₂)₂(2-MeO—Ph) 3-Me-4-MeO—Ph D-16f (CH₂)₂(3-MeO—Ph) 3-Me-5-MeO—Ph D-16g (CH₂)₂(4-MeO—Ph) 2-MeO-3-Me—Ph D-16h CHO 2-MeO-4-Me—Ph D-16i SMe 2-MeO-5-Me—Ph D-16j S(O)Me 2-MeO-6-Me—Ph D-16k S(O)₂Me 3-MeO-4-Me—Ph D-16m SEt 3-MeO-5-Me—Ph D-16n S(O)Et 3,5-(F)₂-4-Me—Ph D-16p S(O)₂Et 3,5-(F)₂-4-MeO—Ph D-17 SPr-n 3,4,5-(MeO)₃—Ph D-17a S(O)Pr-n D-3 D-17b S(O)₂Pr-n D-3a CH₂Ph SPr-i D-4 CH₂(2-MeO—Ph) S(O)Pr-i D-4a CH₂(3-MeO—Ph) S(O)₂Pr-i D-4b CH₂(4-MeO—Ph) SPr-c D-5 CH₂(2,3-(MeO)₂—Ph) S(O)Pr-c

TABLE 20 R^(1a) R^(1a) R^(1a) S(O)₂Pr-c S(O)Pen-t SCHFCH₃ S(D-16) S(O)₂Pen-t SCF₂CH₃ S(O)(D-16) SHex-n SCF(CH₃)₂ S(O)₂(D-16) SHex-c SCF₂CF₂H S(D-16e) SCH₂CH═CH₂ SCF₂CF₃ S(O)(D-16e) S(O)CH₂CH═CH₂ SCF₂CF₂CF₃ S(O)₂(D-16e) S(O)₂CH₂CH═CH₂ SCF(CF₃) SBu-n SCH(Me)CH═CH₂ SCH₂OMe S(O)Bu-n SC(Me)₂CH═CH₂ S(CH₂)₂OMe S(O)₂Bu-n SCH₂CH═CHMe S(O)(CH₂)₂OMe SBu-i SCH₂C(Me)═CH₂ S(O)₂(CH₂)₂OMe S(O)Bu-i S(CH₂)₂CH═CMe₂ SCH(Me)CH₂OMe S(O)₂Bu-i SC(Me)═CH₂ S(O)CH(Me)CH₂OMe SBu-c SC(Me)═CH(Me) S(O)₂CH(Me)CH₂OMe S(O)Bu-c SCH₂C≡CH SCH₂CH(Me)OMe S(O)₂Bu-c S(O)CH₂C≡CH S(O)CH₂CH(Me)OMe SBu-s S(O)₂CH₂C≡CH S(O)₂CH₂CH(Me)OMe S(O)Bu-s SCH(Me)C≡CH SC(Me)₂CH₂OMe S(O)₂Bu-s SC(Me)₂C≡CH S(CH₂)₃OMe SBu-t SCH₂C≡CMe SCH₂OEt S(O)Bu-t SCH₂Cl S(CH₂)₂OEt S(O)₂Bu-t SCH(Me)Cl S(O)(CH₂)₂OEt SPen-n S(CH₂)₂Cl S(O)₂(CH₂)₂OEt S(O)Pen-n S(O)(CH₂)₂Cl SCH(Me)CH₂OEt S(O)₂Pen-n S(O)₂(CH₂)₂Cl SCH₂OPr-i SPen-i SCH(Me)CH₂Cl S(CH₂)₂OPr-i S(O)Pen-i SCH₂CH(Me)Cl S(O)(CH₂)₂OPr-i S(O)₂Pen-i S(CH₂)₃Cl S(O)₂(CH₂)₂OPr-i SPen-c SCF₃ SCH(Me)CH₂OPr-i S(O)Pen-c SCH₂CF₃ SCH₂Pr-c S(O)₂Pen-c S(O)CH₂CF₃ S(O)CH₂Pr-c SPen-s S(O)₂CH₂CF₃ S(O)₂CH₂Pr-c S(O)Pen-s SCH(Me)CF₃ SCH(Me)Pr-c S(O)₂Pen-s S(CH₂)₂CF₃ S(O)CH(Me)Pr-c SPen-t S(CH₂)₃CF₃ S(O)₂CH(Me)Pr-c

TABLE 21 R^(1a) R^(1a) R^(1a) S(CH₂)₂Pr-c SCH(Me)Ph SCH₂(D-8f) SCH₂(D-16) S(O)CH(Me)Ph S(O)₂CH₂(D-8f) S(O)CH₂(D-16) S(O)₂CH(Me)Ph SCH₂(D-8g) S(O)₂CH₂(D-16) SCH₂(2-MeO—Ph) S(O)₂CH₂(D-8g) SCH₂(D-16e) S(O)CH₂(2-MeO—Ph) SCH₂(D-8h) S(O)CH₂(D-16e) S(O)₂CH₂(2-MeO—Ph) S(O)₂CH₂(D-8h) S(O)₂CH₂(D-16e) SCH(Me)(2-MeO—Ph) SCH₂(D-15) SCH₂Bu-c S(O)CH(Me)(2-MeO—Ph) S(O)CH₂(D-15) S(O)CH₂Bu-c S(O)₂CH(Me)(2-MeO—Ph) S(O)₂CH₂(D-15) S(O)₂CH₂Bu-c SCH₂(3-MeO—Ph) SCH(Me)(D-15) SCH(Me)Bu-c S(O)CH₂(3-MeO—Ph) S(O)CH(Me)(D-15) S(CH₂)₂Bu-c S(O)₂CH₂(3-MeO—Ph) S(O)₂CH(Me)(D-15) SCH₂Pen-c SCH(Me)(3-MeO—Ph) S(CH₂)₂(D-15) S(O)CH₂Pen-c S(O)CH(Me)(3-MeO—Ph) S(O)(CH₂)₂(D-15) S(O)₂CH₂Pen-c S(O)₂CH(Me)(3-MeO—Ph) S(O)₂(CH₂)₂(D-15) SCH(Me)Pen-c SCH₂(4-MeO—Ph) NHMe S(CH₂)₂Pen-c S(O)CH₂(4-MeO—Ph) NHEt SCH₂Hex-c S(O)₂CH₂(4-MeO—Ph) NHPr-n SCH(Me)Hex-c SCH(Me)(4-MeO—Ph) NHPr-i S(CH₂)₂Hex-c S(O)CH(Me)(4-MeO—Ph) NHPr-c SCH₂CN S(O)₂CH(Me)(4-MeO—Ph) NH(D-16) S(O)CH₂CN SCH₂(D-8a) NH(D-16e) S(O)₂CH₂CN S(O)CH₂(D-8a) NHBu-n SCH(Me)CN S(O)₂CH₂(D-8a) NHBu-i S(O)CH(Me)CN SCH₂(D-8b) NHBu-c S(O)₂CH(Me)CN S(O)CH₂(D-8b) NHBu-s SC(Me)₂CN S(O)₂CH₂(D-8b) NHBu-t S(O)C(Me)₂CN SCH₂(D-8c) NHPen-n S(O)₂C(Me)₂CN S(O)CH₂(D-8c) NHPen-i S(CH₂)₂CN S(O)₂CH₂(D-8c) NHPen-c S(O)(CH₂)₂CN SCH₂(D-8d) NHPen-s S(O)₂(CH₂)₂CN S(O)CH₂(D-8d) NHPen-t SCH₂Ph S(O)₂CH₂(D-8d) NH(3-Pen) S(O)CH₂Ph SCH₂(D-8e) NHHex-n S(O)₂CH₂Ph S(O)₂CH₂(D-8e) NHHex-c

TABLE 22 R^(1a) R^(1a) R^(1a) N(Me)Me N(Pr-n)Bu-n N(Et)(CH₂)₂OEt N(Me)Et N(Pr-n)Bu-i N(Et)(CH₂)₂OPr-n N(Me)Pr-n N(Pr-n)Bu-c N(Et)(CH₂)₂OPr-i N(Me)Pr-i N(Pr-n)Bu-s N(Pr-n)(CH₂)₂OMe N(Me)Pr-c N(Pr-i)Pr-i N(Pr-n)(CH₂)₂OEt N(Me)(D-16) N(Pr-i)Pr-c N(Pr-n)(CH₂)₂OPr-n N(Me)(D-16e) N(Pr-i)(D-16) N(Pr-n)(CH₂)₂OPr-i N(Me)Bu-n N(Pr-i)(D-16e) N(Pr-i)(CH₂)₂OMe N(Me)Bu-i N(Pr-i)Bu-n N(Pr-i)(CH₂)₂OEt N(Me)Bu-c N(Pr-i)Bu-i N(Pr-i)(CH₂)₂OPr-n N(Me)Bu-s N(Pr-i)Bu-c N(Pr-i)(CH₂)₂OPr-i N(Me)Bu-t N(Pr-i)Bu-s NHCH₂SMe N(Me)Pen-n NHCH₂OMe NHCH₂SEt N(Me)Pen-i NHCH₂OEt NHCH(Me)SMe N(Me)Pen-c NHCH(Me)OMe NHCH(Me)SEt N(Me)Pen-s NHCH(Me)OEt NHC(Me)₂SMe N(Me)Pen-t NHC(Me)₂OMe NHC(Me)₂SEt N(Me)(3-Pen) NHC(Me)₂OEt NH(CH₂)₂SMe N(Me)Hex-n NH(CH₂)₂OMe NH(CH₂)₂S(O)Me N(Me)Hex-c NH(CH₂)₂OEt NH(CH₂)₂S(O)₂Me N(Et)Et NH(CH₂)₂OPr-n NH(CH₂)₂SEt N(Et)Pr-n NH(CH₂)₂OPr-i NH(CH₂)₂S(O)Et N(Et)Pr-i N(Me)CH₂OMe NH(CH₂)₂S(O)₂Et N(Et)Pr-c N(Me)CH₂OEt NH(CH₂)₂SPr-i N(Et)(D-16) N(Me)CH(Me)OMe NH(CH₂)₂S(O)Pr-i N(Et)(D-16e) N(Me)CH(Me)OEt NH(CH₂)₂S(O)₂Pr-i N(Et)Bu-n N(Me)C(Me)₂OMe N(Me)CH₂SMe N(Et)Bu-i N(Me)C(Me)₂OEt N(Me)CH₂SEt N(Et)Bu-c N(Me)(CH₂)₂OMe N(Me)CH(Me)SMe N(Et)Bu-s N(Me)(CH₂)₂OEt N(Me)CH(Me)SEt N(Pr-n)Pr-n N(Me)(CH₂)₂OPr-n N(Me)C(Me)₂SMe N(Pr-n)Pr-i N(Me)(CH₂)₂OPr-i N(Me)C(Me)₂SEt N(Pr-n)Pr-c N(Et)C(Me)₂OMe N(Me)(CH₂)₂SMe N(Pr-n)(D-16) N(Et)C(Me)₂OEt N(Me)(CH₂)₂S(O)Me N(Pr-n)(D-16e) N(Et)(CH₂)₂OMe N(Me)(CH₂)₂S(O)₂Me

TABLE 23 R^(1a) R^(1a) N(Me)(CH₂)₂SEt NH(4-MeO—Ph) N(Me)(CH₂)₂S(O)Et NH(2,3-(MeO)₂—Ph) N(Me)(CH₂)₂S(O)₂Et NH(2,4-(MeO)₂—Ph) N(Me)(CH₂)₂SPr-i NH(2,5-(MeO)₂—Ph) N(Me)(CH₂)₂S(O)Pr-i NH(2,6-(MeO)₂—Ph) N(Me)(CH₂)₂S(O)₂Pr-i NH(3,4-(MeO)₂—Ph) NHCF₂H NH(3,5-(MeO)₂—Ph) NHCF₃ N(Me)Ph NHCH₂CF₂H N(Me)(2-MeO—Ph) NHCH₂CF₃ N(Me)(3-MeO—Ph) NH(CH₂)₂CF₃ N(Me)(4-MeO—Ph) NH(CH₂)₂Cl N(Me)(2,3-(MeO)₂—Ph) NH(CH₂)₃Cl N(Me)(2,4-(MeO)₂—Ph) N(Me)CF₂H N(Me)(2,5-(MeO)₂—Ph) N(Me)CF₃ N(Me)(2,6-(MeO)₂—Ph) N(Me)CH₂CF₂H N(Me)(3,4-(MeO)₂—Ph) N(Me)CH₂CF₃ N(Me)(3,5-(MeO)₂—Ph) N(Me)(CH₂)₂CF₃ N(Me)(CH₂)₂Cl N(Me)(CH₂)₃Cl NHCH₂CH═CH₂ N(Me)CH₂CH═CH₂ NHCH₂C≡CH NHCH₂C≡CMe N(Me)CH₂C≡CH N(Me)CH₂C≡CMe NHCH₂CN NH(CH₂)₂CN NH(CH₂)₃CN N(Me)CH₂CN N(Me)(CH₂)₂CN N(Me)(CH₂)₃CN NHPh NH(2-MeO—Ph) NH(3-MeO—Ph)

THIRD TABLE

TABLE 24 R^(2a) R^(1b) CF₂H Me CF₂H Et CF₂H Pr-n CF₂H Pr-i CF₂H Pr-c CF₂H Bu-n CF₂H Bu-i CF₂H Bu-c CF₂H Bu-s CF₂H Bu-t CF₂H Pen-n CF₂H Pen-i CF₂H Pen-c CF₂H Pen-s CF₂H Pen-t CF₂H 3-Pen CF₂H Hex-n CF₂H Hex-c CF₂H CH₂Ph CF₂H CH(Me)Ph CF₂H (CH₂)₂Ph CF₂H (CH₂)₃Ph CF₂Cl Me CF₂Cl Et CF₂Cl Pr-n CF₂Cl Pr-i CF₂Cl Pr-c CF₂Cl Bu-n CF₂Cl Bu-i CF₂Cl Bu-c CF₂Cl Bu-s CF₂Cl Bu-t CF₂Cl Pen-n CF₂Cl Pen-i CF₂Cl Pen-c CF₂Cl Pen-s CF₂Cl Pen-t CF₂Cl 3-Pen CF₂Cl Hex-n CF₂Cl Hex-c CF₂Cl CH₂Ph CF₂Cl CH(Me)Ph CF₂Cl (CH₂)₂Ph CF₂Cl (CH₂)₃Ph CF₂Br Me CF₂Br Et CF₂Br Pr-n CF₂Br Pr-i CF₂Br Pr-c CF₂Br Bu-n CF₂Br Bu-i CF₂Br Bu-c CF₂Br Bu-s CF₂Br Bu-t CF₂Br CH₂Ph CF₂Br CH(Me)Ph CF₃ Me CF₃ Et CF₃ Pr-n CF₃ Pr-i CF₃ Pr-c CF₃ Bu-n CF₃ Bu-i CF₃ Bu-c CF₃ Bu-s CF₃ Bu-t CF₃ Pen-n CF₃ Pen-i

TABLE 25 R^(2a) R^(1b) CF₃ Pen-c CF₃ Pen-s CF₃ Pen-t CF₃ 3-Pen CF₃ Hex-n CF₃ Hex-c CF₃ CH₂Ph CF₃ CH(Me)Ph CF₃ (CH₂)₂Ph CF₃ (CH₂)₃Ph CH₂CF₂H Me CH₂CF₂H Et CH₂CF₂H Pr-n CH₂CF₂H Pr-i CH₂CF₂H Pr-c CH₂CF₂H Bu-n CH₂CF₂H Bu-i CH₂CF₂H Bu-c CH₂CF₂H Bu-s CH₂CF₂H Bu-t CH₂CF₂H CH₂Ph CH₂CF₂H CH(Me)Ph CH₂CF₃ Me CH₂CF₃ Et CH₂CF₃ Pr-n CH₂CF₃ Pr-i CH₂CF₃ Pr-c CH₂CF₃ Bu-n CH₂CF₃ Bu-i CH₂CF₃ Bu-c CH₂CF₃ Bu-s CH₂CF₃ Bu-t CH₂CF₃ CH₂Ph CH₂CF₃ CH(Me)Ph CHFCH₃ Me CHFCH₃ Et CHFCH₃ Pr-n CHFCH₃ Pr-i CHFCH₃ Pr-c CHFCH₃ Bu-n CHFCH₃ Bu-i CHFCH₃ Bu-c CHFCH₃ Bu-s CHFCH₃ Bu-t CHFCH₃ CH₂Ph CHFCH₃ CH(Me)Ph CF₂CH₃ Me CF₂CH₃ Et CF₂CH₃ Pr-n CF₂CH₃ Pr-i CF₂CH₃ Pr-c CF₂CH₃ Bu-n CF₂CH₃ Bu-i CF₂CH₃ Bu-c CF₂CH₃ Bu-s CF₂CH₃ Bu-t CF₂CH₃ CH₂Ph CF₂CH₃ CH(Me)Ph CF(CH₃)₂ Me CF(CH₃)₂ Et CF(CH₃)₂ Pr-n CF(CH₃)₂ Pr-i CF(CH₃)₂ Pr-c CF(CH₃)₂ Bu-n CF(CH₃)₂ Bu-i CF(CH₃)₂ Bu-c CF(CH₃)₂ Bu-s CF(CH₃)₂ Bu-t

TABLE 26 R^(2a) R^(1b) CF(CH₃)₂ CH₂Ph CF(CH₃)₂ CH(Me)Ph CF₂CF₂H Me CF₂CF₂H Et CF₂CF₂H Pr-n CF₂CF₂H Pr-i CF₂CF₂H Pr-c CF₂CF₂H Bu-n CF₂CF₂H Bu-i CF₂CF₂H Bu-c CF₂CF₂H Bu-s CF₂CF₂H Bu-t CF₂CF₂H Pen-n CF₂CF₂H Pen-i CF₂CF₂H Pen-c CF₂CF₂H Pen-s CF₂CF₂H Pen-t CF₂CF₂H 3-Pen CF₂CF₂H Hex-n CF₂CF₂H Hex-c CF₂CF₂H CH₂Ph CF₂CF₂H CH(Me)Ph CF₂CF₂H (CH₂)₂Ph CF₂CF₂H (CH₂)₃Ph CF₂CF₃ Me CF₂CF₃ Et CF₂CF₃ Pr-n CF₂CF₃ Pr-i CF₂CF₃ Pr-c CF₂CF₃ Bu-n CF₂CF₃ Bu-i CF₂CF₃ Bu-c CF₂CF₃ Bu-s CF₂CF₃ Bu-t CF₂CF₃ Pen-n CF₂CF₃ Pen-i CF₂CF₃ Pen-c CF₂CF₃ Pen-s CF₂CF₃ Pen-t CF₂CF₃ 3-Pen CF₂CF₃ Hex-n CF₂CF₃ Hex-c CF₂CF₃ CH₂Ph CF₂CF₃ CH(Me)Ph CF₂CF₃ (CH₂)₂Ph CF₂CF₃ (CH₂)₃Ph CF₂CF₂CF₃ Me CF₂CF₂CF₃ Et CF₂CF₂CF₃ Pr-n CF₂CF₂CF₃ Pr-i CF₂CF₂CF₃ Pr-c CF₂CF₂CF₃ Bu-n CF₂CF₂CF₃ Bu-i CF₂CF₂CF₃ Bu-s CF₂CF₂CF₃ Bu-t CF(CF₃)₂ Me CF(CF₃)₂ Et CF(CF₃)₂ Pr-n CF(CF₃)₂ Pr-i CF(CF₃)₂ Pr-c CF(CF₃)₂ Bu-n CF(CF₃)₂ Bu-i CF(CF₃)₂ Bu-s CF(CF₃)₂ Bu-t

The compound of the present invention can be used in both treatment methods of soil application and foliage application under flooding as a herbicide for paddy fields. Examples of paddy field weeds may include Potamogetonaceae weeds represented by Potamogeton distinctus; Alismataceae weeds represented by Alisma canaliculatum, Sagittaria pygmaea, and Sagittaria trifolia; Gramineae weeds represented by Leptochloa chinensis, Echinochloa crus-galli, Echinochloa oryzicola, Homalocenchrus japonocus, and Paspalum distichum; Cyperaceae weeds represented by Eleocharis kuroguwai, Scirpus juncoides, Scirpus nipponicus, Cyperus serotinus, Cyperus difformis, and Cyperus hakonensis; Lemnaceae weeds represented by Spirodela polyrhiza and Lemna paucicostata; Commelinaceae weeds represented by Murdannia keisak; Pontederiaceae weeds represented by Monochoria korsakowii and Monochoria vaginalis; Elatinaceae weeds represented by Elatine triandra; Lythraceae weeds represented by Ammannia multiflora and Rotala indica; Oenotheraceae weeds represented by Lidwigia epilobioides; Scrophulariaceae weeds represented by Dopatrium junceum, Gratiola japonica, Limnophila sessilifolia, Lindernia pyxidaria, and Lindernia dubia; Leguminosae weeds such as Aeschynomene indica, and Compositae weeds represented by, Bidens frondosa and Bidens tripartita and the like.

The compound of the present invention can be used in any treatment methods of soil treatment, soil incorporation treatment, and foliage treatment as a herbicide for dry fields and orchards. Examples of the dry field weeds may include broad-leaved weeds such as Solanaceae weeds represented by Solanum nigrum and Datura stramonium; Geraniaceae weeds represented by Granium carolinianum; Malvaceae weeds represented by Abutilon theophrasti and Sida spinosa; Convolvulaceae weeds represented by Ipomoea spps. such as Ipomoea purpurea and Calystegia spps.; Amaranthaceae weeds represented by Amaranthus lividus and Amaranthus retroexus; Compositae weeds represented by Xanthium pensylvanicum, Ambrosia artemisiaefolia, Helianthus annuus, Galinsoga ciliata, Cirsium arvense, Senecio vulgaris, and Erigeron annuus; Cruciferae weeds represented by Rorippa indica, Sinapis arvensis, and Capsella Bursapastoris; Polygonaceae weeds represented by Polygonum Blumei and Polygonum convolvulus; Portulacaceae weeds represented by Portulaca oleracea; Chenopodiaceae weeds represented by Chenopodium album, Chenopodium ficifolium, and Kochia scoparia; Caryophyllaceae weeds represented by Stellaria media; Scrophulariaceae weeds represented by Veronica persica; Commelinaceae weeds represented by Commelina communis; Labiatae weeds represented by Lamium amplexicaule and Lamium purpureum; Euphorbiaceae weeds represented by Euphorbia supina and Euphorbia maculate; Rubiaceae weeds represented by Galium spurium and Rubia akane; Violaceae weeds represented by Viola mandshurica; Leguminosae weeds represented by Sesbania exaltata and Cassia obtusifolia; and Oxsaldaseae represented by Oxsalis courniculata; Graminaceous weeds represented by Sorgham bicolor, Panicum dichotomiflorum, Sorghum halepense, Echinochloa crus-galli var. crus-galli, Echinochloa crus-galli var. praticola, Echinochloa utilis, Digitaria ciliaris, Avena fatua, Alopecurus myosuroides, Eleusine indica, Setaria viridis, Setaria faberi, and Alopecurus aegualis; and Cyperaceous weeds represented by Cyperus rotundus and Cyperus esculentus and the like.

The compound of the present invention can be used in any treatment methods of soil treatment, soil incorporation treatment, and foliage treatment in non-agricultural lands such as turfs, play grounds, open grounds, road verges, and railway verges other than the agricultural and horticultural fields such as paddy fields, dry fields, and orchards. As weeds in these non-agricultural lands, the following examples of the weeds are exemplified in addition to those described as weeds in dry fields and orchards. Examples of the weed may include Poa annua, Taraxacum officinale, Conyza sumatrensis, Cardamine flexuosa, Trifolium repens, Hydrocotyle sibthorpioides, Plantago asiatica, Cyperus brevifolius, Kyllinga brevifolia, and Equisetum arvense and the like.

When the compound of the present invention is applied as the herbicide, the compound is usually mixed with an appropriate solid carrier or liquid carrier, and surfactants, penetrating agents, spreading agents, thickeners, antifreeze agents, binders, anti-caking agents, disintegrating agents stabilizing agents and the like are added, if desired. The herbicide can be applied to practical uses by any herbicide formulation of the herbicide form such as water-dispersible agents, emulsion agents, flowable agents, dry-flowable agents, liquid agents, powder agents, granule agents, or gel agents. From the viewpoint of labor saving and improvement in safety, any of the herbicide formulation of the herbicide form can be applied in an encapsulated state in a water-soluble package.

Examples of the solid carriers may include natural minerals such as quartz, kaolinite, pyrophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite, and diatomaceous earth; inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate and potassium chloride; and synthetic silicic acid and synthetic silicates.

Examples of the liquid carriers may include alcohols such as ethylene glycol, propylene glycol, and isopropanol; aromatic hydrocarbons such as xylene, alkylbenzene, and alkylnaphthalene; ethers such as butylcellosolve; ketones such as cyclohexanone; esters such as y-butyrolactone; acid amides such as N-methylpyrrolidone and N-octylpyrrolidone; vegetable oils such as soybean oil, rapeseed oil, cotton seed oil, and castor oil; and water.

These solid carriers and liquid carriers may be used singly or in combination of two or more of them.

Examples of the surfactant may include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene styrylphenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters; anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, lignin sulfonates, alkyl sulfosuccinates, naphthalene sulfonate, alkylnaphthalene sulfonates, salts of formalin condensate of naphthalene sulfonic acid, salts of formalin condensate of alkylnaphthalene sulfonic acid, polyoxyethylene alkylaryl ether sulfates and phosphates, polyoxyethylene styrylphenyl ether sulfates and phosphates, polycarboxylates, and polystyrene sulfonates; cationic surfactants such as alkylamine salts and alkyl quaternary ammonium salts; and amphoteric surfactants such as amino acid-type surfactants and betaine-type surfactants.

The content of the surfactants is not particularly limited. Usually, the content is preferably in a range of 0.05 parts by weight to 20 parts by weight relative to 100 parts by weight of the herbicide formulation of the present invention. These surfactants may be used singly or in combination of two or more of them.

The compound of the present invention may be applied in a mixed state with another herbicide, various insecticides, a bactericide, a plant growth regulator, a synergist, or the like at the time of herbicide formulation or application.

In particular, by applying the herbicide in a mixed state with another herbicide, reduction in cost by reduction in an application amount, expansion in herbicidal spectrum by synergistic action of mixed herbicides, and a higher herbicidal effect can be expected. At this time, a combination of a plurality of known herbicides at the same time is also possible.

Examples of the preferable herbicide used in a mixture with the compound of the present invention may include acetochlor/general name, acifluorfen/general name, aclonifen/general name, alachlor/general name, alloxydim/general name, alloxydim-sodium/general name, ametryn/general name, amicarbazone/general name, amidosulfuron/general name, aminocyclopirachlor/general name, aminocyclopirachlor-salts and esters, aminopyralid/general name, aminopyralid-salts and esters, amiprophos-methyl/general name, amitrol/general name, anilofos/general name, asulam/general name, atrazine/general name, azafenidin/general name, azimsulfuron/general name, beflubutamid/general name, benazolin-ethyl/general name, bencarbazone/general name, benfluralin (benefin)/general name, benfuresate/general name, bensulfuron-methyl/general name, bensulide/general name, bentazone/general name, bentazone-sodium/general name, bentazone-salts, benthiocarb/general name, benzfendizone/general name, benzobicyclon/general name, benzofenap/general name, bialaphos/general name, bialaphos-sodium/general name, bicyclopyrone/general name, bifenox/general name, bispyribac/general name, bispyribac-sodium/general name, bromacil/general name, bromobutide/general name, bromofenoxim/general name, bromoxynil/general name, bromoxynil-salts and esters, butachlor/general name, butafenacil/general name, butamifos/general name, butenachlor/general name, butralin/general name, butroxydim/general name, butylate/general name, cafenstrole/general name, carbetamide/general name, carfentrazone-ethyl, chlomethoxyfen/general name, chlomethoxynil/general name, chloramben/general name, chloramben-salts and esters, chloransulam-methyl/general name, chlorflurenol-methyl/general name, chloridazon/general name, chlorimuron-ethyl/general name, chlorobromuron/general name, chlorotoluron/general name, chloroxuron/general name, chlorphtalim/general name, chlorpropham/general name, chlorpropham/general name, chlorsulfuron/general name, chlorthal-dimethyl/general name, chlorthiamid/general name, cinidon-ethyl/general name, cinmethylin/general name, cinosulfuron/general name, clethodim/general name, clodinafop/general name, clodinafop-propargyl/general name, clomazone/general name, clomeprop/general name, clopyralid/general name, clopyralid-salts and esters, CNP/general name, cumyluron/general name, cyanazin/general name, cycloate/general name, cyclopyrimorate/general name (SW-065/test name), cyclosulfamuron/general name, cycloxydim/general name, cyhalofop-butyl/general name, DAH-500/test name, dalapon/general name, dazomet/general name, desmedipham/general name, desmetryn/general name, dicamba/general name, dicamba-salts and esters, dichlobenil/general name, diclofop/general name, diclofop-methyl/general name, dichlorprop/general name, dichlorprop-salts and esters, dichlorprop-P/general name, dichlorprop-P-salts and esters, diclosulam/general name, difenzoquat/general name, diflufenican/general name, diflufenzopyr/general name, diflufenzopyr-sodium/general name, dimepiperate/general name, dimethametryn/general name, dimethachlor/general name, dimethenamid/general name, dimethenamid-p/general name, dimethipin/general name, dinitramine/general name, dinoseb/general name, dinoterb/general name, DNOC/general name, diphenamid/general name, diquqt/general name, dithiopyl/general name, diuron/general name, DSMA/general name, dymron/general name, endothal/general name, EPTC/general name, esprocarb/general name, ethalfluralin/general name, ethametsulfuron-methyl/general name, ethofumesate/general name, etobenzanid/general name, ethoxysulfuron/general name, flazasulfuron/general name, fenoxaprop/general name, fenoxaprop-ethyl/general name, fenoxasulfone/general name, fenquionotrion/general name, fentrazamide/general name, flamprop/general name, flazasulfuron/general name, florasulam/general name, fluazifop/general name, fluazifop-butyl/general name, fluazolate/general name, flucarbazone-sodium/general name, flucetosulfuron/general name, flucloralin/general name, flufenacet/general name, flufenpyl-ethyl/general name, flumetsulam/general name, flumiclorac-pentyl/general name, flumioxazin/general name, fluometuron general name, fluoroglycofen-ethyl/general name, flupyrsulfuron/general name, flupoxam/general name, flurenol/general name, fluridone/general name, flurochloridone/general name, fluroxypyr/general name, fluroxypyr-esters, flurprimidol/general name, flurtamone/general name, fluthiacet-methyl/general name, fomesafen/general name, foramsulfuron/general name, fosamine/general name, glufosinate/general name, glufosinate-ammonium/general name, glyphosate/general name, glyphosate-ammonium/general name, glyphosate-iso-propylammonium/general name, glyphosate-potassium/general name, glyphosate-sodium/general name, glyphosate-trimesium/general name, halauxifen/general name, halauxifen-salts and esters, halosafen/general name, halosulfuron/general name, halosulfuron-methyl general name, haloxyfop/general name, haloxyfop-methyl/general name, hexazinone general name, imazamethabenz-methyl/general name, imazamox/general name, imazapic/general name, imazapyr/general name, imazethapyr/general name, imazaquin/general name, imazosulfuron/general name, indanofan/general name, indaziflam/general name, iodosulfuron-methyl-sodium/general name, ioxynil octanoate/general name, ioxynil-salts and esters, ipfencarbazone/general name, isoproturon general name, isouron/general name, isoxaben/general name, isoxaflutole/general name, karbutilate/general name, lactofen/general name, lenacil/general name, linuron/general name, maleic hydrazide/general name, MCPA/general name, MCPA-salts and esters, MCPB/general name, MCPB-salts and esters, mecoprop (MCPP)/general name, mecoprop-salts and esters, mecoprop-P (MCPP-P)/general name, mecoprop-P-salts and esters, mefenacet/general name, mefluidide/general name, mesosulfuron-methyl general name, mesotrione/general name, metam/general name, metamifop/general name, metamitron/general name, metazachlor/general name, methabenzthiazuron general name, metazosulfuron/general name, methiozolin/general name, methyl azide general name, methyl bromide/general name, methyl dymron/general name, methyl iodide/general name, metobenzuron/general name, metolachlor/general name, metolachlor-S/general name, metosulam/general name, metribuzin/general name, metsulfuron-methyl/general name, metoxuron/general name, molinate/general name, monolinuron/general name, monosulfuron/general name, monosulfuron-methyl general name, MSMA/general name, naproanilide/general name, napropamide general name, naptalam/general name, naptalam-sodium/general name, neburon general name, nicosulfuron/general name, norflurazon/general name, OK-701/test name, oleic acid/general name, orbencarb/general name, orthosulfamuron/general name, oryzalin/general name, oxadiargyl/general name, oxadiazon/general name, oxasulfuron/general name, oxaziclomefone/general name, oxyfluorfen/general name, paraquat/general name, pelargonicacid/general name, pendimethalin/general name, penoxsulam/general name, pentanochlor/general name, pentoxazone/general name, pethoxamid/general name, phenmedipham-ethyl/general name, picloram/general name, picloram-salts and esters, picolinafen/general name, pinoxaden/general name, piperophos/general name, pretilachlor/general name, primisulfuron-methyl/general name, prodiamine/general name, profluazol/general name, profoxydim/general name, prometon/general name, prometryn/general name, propachlor/general name, propanil/general name, propaquizafop/general name, propazin/general name, propham general name, propisochlor/general name, propoxycarbazone-sodium/general name, propyrisulfuron/general name, propyzamide/general name, prosulfocarb/general name, prosulfuron/general name, pyraclonil/general name, pyraflufen-ethyl/general name, pyrasulfotole/general name, pyrazolynate/general name, pyrazosulfuron/general name, pyrazosulfuron-ethyl/general name, pyrazoxyfen/general name, pyribenzoxim/general name, pyributicarb/general name, pyridafol/general name, pyridate/general name, pyriftalid/general name, pyriminobac-methyl/general name, pyrimisulfan/general name, pyrithiobac-sodium/general name, pyroxasulfone/general name, pyroxsulam general name, quinclorac/general name, quinmerac/general name, quinoclamine general name, quizalo fop/general name, quizalo fop-ethyl/general name, quizalofop-tefuryl/general name, quizalofop-P/general name, quizalofop-P-ethyl general name, quizalofop-P-tefuryl/general name, rimsulfuron/general name, saflufenacil/general name, sethoxydim/general name, siduron/general name, simazine/general name, simetryn/general name, SL-261/test name, sulcotrione/general name, sulfentrazone/general name, sulfometuron-methyl/general name, sulfosulfuron general name, TCBA (2,3,6-TBA)/general name, 2,3,6-TBA-salts and esters, TCTP (chlorthal-dimethyl, tetorachlorothiophene)/general name, tebutam/general name, tebuthiuron/general name, tefuryltrione/general name, tembotrione/general name, tepraloxydim/general name, terbacil/general name, terbumeton/general name, terbuthylazine/general name, terbutryn/general name, tetrapion (flupropanate)/general name, thenylchlor/general name, thiazafluron/general name, thiazopyr/general name, thidiazimin/general name, thidiazuron/general name, thiencarbazone-methyl/general name, thifensulfuron-methyl/general name, tolpyralate/general name, topramezon general name, tralkoxydim/general name, triafamone/general name, triallate/general name, triasulfuron/general name, triaziflam/general name, tribenuron-methyl/general name, triclopyr/general name, triclopyr-salts and esters, tridiphane/general name, trietazine/general name, trifludimoxadin/general name, trifloxysulfuron/general name, trifluralin/general name, triflusulfuron-methyl/general name, tritosulfuron/general name, 2,4-PA/general name, 2,4-PA-salts and esters, 2,4-DB/general name, and 2,4-DB-salts and esters. These components may be used singly or in combination of two or more of them. When these components are mixed, the mixing ratio may be freely selected.

Examples of safeners may include AD-67, benoxacor/general name, cloquintocet-mexyl/general name, cyomerinil/general name, dichlormid/general name, dicyclonone/general name, cyprosulfamide/general name, diethorate/general name, DKA-24, dymron/general name, fenclorazole-ethyl/general name, fenclorim/general name, HEXIM/general name, flurazole/general name, fluxofenim/general name, furilazole/general name, isoxadifen/general name, isoxadifen-ethyl/general name, MCPA, mecoprop/general name, mefenpyr/general name, mefenpyr-ethyl/general name, mefenpyr-diethyl/general name, mephenate/general name, MG-191, NA (Naphthalic anhydride), OM (Octamethylene-diamine), oxabetrinil/general name, PPG-1292, and R-29148. These agricultural chemical active components may be used singly or in combination of two or more of them. When these components are mixed, the mixing ratio may be freely selected.

Although the application amount of the compound of the present invention varies depending on the application situation, the application time, the application method, the cultivated crop and the like, the appropriate application amount is generally 0.005 kg/ha to 50 kg/ha as the amount of the active component.

Next, the formulation examples of the herbicide formulations when the compound of the present invention is used will be described. However, the formulation examples of the present invention are not limited to these examples. Hereinafter, the term “part” in the formulation examples means part by weight.

Water-Dispersible Agent

Compound of the present invention 0.1 parts to 80 parts Solid carrier   5 parts to 98.9 parts Surfactant    1 part to 10 parts Others   0 parts to 5 parts

Examples of Others may include anti-caking agents, stabilizing agents and the like.

Emulsion Agent

Compound of the present invention 0.1 parts to 30 parts Liquid carrier  45 parts to 95 parts Surfactant 4.9 parts to 15 parts Others   0 parts to 10 parts

Examples of Others may include spreading agents, stabilizing agents and the like.

Flowable Agent

Compound of the present invention  0.1 parts to 70 parts Liquid carrier   15 parts to 98.89 parts Surfactant    1 part to 12 parts Others 0.01 parts to 30 parts

Examples of Others may include antifreeze agents, thickeners and the like.

Dry Flowable Agent

Compound of the present invention 0.1 parts to 90 parts Solid carrier   0 parts to 98.9 parts Surfactant    1 part to 20 parts Others   0 parts to 10 parts

Examples of Others may include binders, stabilizing agents and the like.

Liquid Agent

Compound of the present invention 0.01 parts to 70 parts Liquid carrier   20 parts to 99.99 parts Others   0 parts to 10 parts

Examples of Others may include antifreeze agents, spreading agents and the like.

Granule Agent

Compound of the present invention 0.01 parts to 80 parts Solid carrier   10 parts to 99.99 parts Others   0 parts to 10 parts

Examples of Others may include binders, stabilizing agents and the like.

Powder Agent

Compound of the present invention 0.01 parts to 30 parts Solid carrier   65 parts to 99.99 parts Others   0 parts to 10 parts

Examples of Others may include anti-drift agents, stabilizing agents and the like.

When the agents are used, the herbicide formulation is applied without any treatment or by diluting the agent to 1 to 10,000 times with water.

Herbicide Formulation Example

Next, examples of agricultural chemical formulation containing the compound of the present invention as the active component will be descried. The present invention, however, is not limited to these examples. Hereinafter, the term “part” in the formulation examples means part by weight.

Formulation Example 1 Water-Dispersible Agent

Compound of the present invention No. 1-001 20 parts Pyrophyllite 76 parts Sorpol 5039  2 parts (Anionic surfactant: manufactured by TOHO Chemical Industry Co., Ltd., trade name) CARPLEX #80  2 parts (Synthetic hydrated silicic acid: Shionogi & Co., Ltd., trade name)

The above components are uniformly mixed and pulverized to give the water-dispersible agent.

Formulation Example 2 Emulsion Agent

Compound of the present invention No. 1-001  5 parts Xylene 75 parts N-methylpyrrolidone 15 parts Sorpol 2680  5 parts (Anionic surfactant: manufactured by TOHO Chemical Industry Co., Ltd., trade name)

The above components are mixed to give the emulsion agent.

Formulation Example 3 Flowable Agent

Compound of the present invention No. 1-001 25 parts Agrisol S-710 10 parts (Nonionic surfactant: Kao Corporation, trade name) Lunox 1000C 0.5 parts (Anionic surfactant: manufactured by TOHO Chemical Industry Co., Ltd., trade name) Xanthane gum 0.02 parts Water 64.48 Parts

After the above components are uniformly mixed, the mixture was wet-pulverized to give the flowable agent.

Formulation Example 4 Dry Flowable Agent

Compound of the present invention No. 1-001 75 parts HITENOL NE-15  5 parts (Anionic surfactant: manufactured by DKS Co. Ltd., trade name) Vanillex N 10 parts (Anionic surfactant: manufactured by NIPPON PAPER INDUSTRIES CO., LTD., trade name) CARPLEX #80 10 parts (Synthetic hydrated silicic acid: Shionogi & Co., Ltd., trade name)

The above components are uniformly mixed and pulverized and then a small amount of water was added to the mixture to stir, to mix, and to knead. The resultant mixture was granulated with an extruding-type granulator. The granules are dried to form the dry flowable agent.

Formulation Example 5 Granular Agent

Compound of the present invention No. 1-001  1 part Bentonite 55 parts Talc 44 parts

The above components are uniformly mixed and pulverized and then a small amount of water was added to the mixture to stir, to mix, and to knead. The resultant mixture was granulated with an extruding-type granulator. The granules are dried to give the granular agent.

EXAMPLES

Hereinafter the present invention will be further described in detail by specifically describing Synthesis Examples and Test Examples of the heterocyclic amide compounds of Formula (1) in the present invention as Examples. The present invention, however, is not limited to these Examples.

As a medium pressure preparative liquid chromatography described in Synthesis Examples and Reference Examples, Medium pressure preparative apparatus; YFLC-Wprep (flow rate: 18 ml/min, 40 μm silica gel packed column) manufactured by Yamazen Corporation was used.

The chemical shift values of proton nuclear magnetic resonance in Examples were measured at 300 MHz using Me₄Si (tetramethylsilane) as a reference substance. Solvents used in measurement are described in Synthesis Examples below. The symbols of the chemical shift values of proton nuclear magnetic resonance in Examples have the following meanings.

s: singlet, d: doublet, t: triplet, m: multiplet, q: quartet, and br: broad

SYNTHESIS EXAMPLES Synthesis Example 1 3-Isopropyl-5-methyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide (compound No. 1-003) Step 1; Synthesis of methyl 2-hydrazinyl-6-methylnicotinate

To the mixed solution of 3.0 g (16.2 mmol) of methyl 2-chloro-6-methylnicotinate and 30 ml of dioxane, 1.62 g (32.3 mmol) of hydrazine monohydrate was added at room temperature. After completion of the addition, the reaction mixture was stirred at 60° C. for 4 hours and subsequently 80° C. for 6 hours. After completion of stirring, the reaction was terminated by adding water and the reaction liquid was extracted with ethyl acetate (150 ml, 2 times). The obtained organic phase was washed with a saturated sodium bicarbonate aqueous solution. Thereafter, the organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and then anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with hexane and filtered to give 1.60 g of the target product as an orange solid.

Melting point: 90° C. to 91° C.

Step 2; Synthesis of methyl 2-(2-isobutyrylhydrazinyl)-6-methylnicotinate

To the mixed solution of 1.5 g (8.28 mmol) of methyl 2-hydrazinyl-6-methylnicotinate, 838 mg (8.28 mmol) of triethylamine, and 20 ml of tetrahydrofuran, 882 mg (8.28 mmol) of isobutyryl chloride was added under cooling with ice. After completion of the addition, the reaction mixture was stirred for 30 minutes under cooling with ice. After completion of stirring, the reaction was terminated by adding water and the reaction liquid was extracted with ethyl acetate (100 ml, 1 time). The obtained organic phase was washed with water. Thereafter, the organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and then anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with hexane and diisopropyl ether and filtered to give 1.68 g of the target product as a flesh-colored solid.

Melting point: 99° C. to 101° C.

Step 3; Synthesis of methyl 3-isopropyl-5-methyl-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

To the mixed solution of 1.6 g (63.7 mmol) of methyl 2-(2-isobutyrylhydrazinyl)-6-methylnicotinate and 10 ml of toluene, 3 ml of phosphoryl chloride was added at room temperature. After completion of the addition, the reaction mixture was stirred for 5 hours under heating to reflux. After completion of stirring, the reaction mixture was added to ice-water to terminate the reaction. Thereafter, the reaction liquid was washed with ethyl acetate (50 ml, 1 time). To the obtained aqueous phase, potassium carbonate was added under cooling with ice to adjust the pH to 8 to 9. Thereafter, the reaction liquid was extracted with ethyl acetate (100 ml, 2 times). The obtained organic phase was dried over anhydrous sodium sulfate and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 490 mg of the target product as a light yellow solid.

Melting point: 138° C. to 140° C.

Step 4; Synthesis of 3-isopropyl-5-methyl-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

To the mixed solution of 450 mg (1.93 mmol) of methyl 3-isopropyl-5-methyl-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate and 4 ml of methanol, 2 ml of 1 M sodium hydroxide aqueous solution was added at room temperature. After completion of the addition, the reaction mixture was stirred for 2 hours at room temperature. After completion of stirring, 1 M hydrochloric acid was added to adjust the pH to 2 to 3. After the solvent in the reaction liquid was distilled away under reduced pressure, the precipitated solid was washed with water and filtered to give 250 mg of the target product as a light yellow solid.

Melting point: 194° C. to 195° C.

Step 5; Synthesis of 3-isopropyl-5-methyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide

To a mixed solvent of 400 mg (1.95 mmol) of 3-isopropyl-5-methyl-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid, 0.1 ml of N,N-dimethylformamide, and 3 ml of methylene chloride, 463 mg (3.91 mmol) of oxalyl chloride was added at room temperature. After completion of the addition, the reaction mixture was stirred for 1 hour at room temperature. After completion of stirring, the solvent in the reaction mixture was distilled away under reduced pressure to give crude 3-isopropyl-5-methyl-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid chloride hydrochloride. To the mixed solution of 540 mg (1.95 mmol) of the obtained crude 3-isopropyl-5-methyl-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid chloride hydrochloride, 180 mg (1.82 mmol) of 5-methyl-1,3,4-oxadiazol-2-amine and 5 ml of methylene chloride, 368 mg (3.91 mmol) of triethylamine was added under cooling with ice. After completion of the addition, the reaction mixture was stirred for 20 hours at room temperature. After completion of stirring, 5 ml of pyridine and 10 mg of 4-(dimethylamino)pyridine were added to reaction mixture. Thereafter, the resultant reaction mixture was stirred at 60° C. for 10 hours. After completion of stirring, the reaction was terminated by adding water and the reaction liquid was extracted with ethyl acetate (20 ml, 1 time). The obtained organic phase was washed with water. Thereafter, the organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and anhydrous sodium sulfate and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and ethyl acetate and filtered to give 60 mg of the target product as a brown solid.

Synthesis Example 2 3-Isopropyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4, 3-a]pyridine-8-carboxamide (Compound No. 1-004)

To the mixed solution of 160 mg (0.59 mmol) of 3-isopropyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid, 70 mg (0.71 mmol) of 5-methyl-1,3,4-oxadiazol-2-amine, and 5 ml of N,N-dimethylformamide, 135 mg (0.71 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 96 mg (0.71 mmol) of 1-hydroxy-7-azabenzotriazole were added. After completion of the addition, the reaction mixture was stirred for 24 hours at room temperature. After completion of stirring, the reaction was terminated by adding water and the reaction liquid was extracted with chloroform (100 ml, 1 time). The obtained organic phase was washed with water. Thereafter, the organic phase was dried over anhydrous sodium sulfate and the solvent was distilled away under reduced pressure. The obtained residue was purified with silica gel chromatography {n-hexane:ethyl acetate=1:1 to 0:1 (volume ratio; the same applies hereafter)} to give 90 mg of the target product as a white solid.

Melting point: 176° C. to 178° C.

Synthesis Example 3 3-Isopropyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(methylthio)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide (Compound No. 1-009) Step 1; Synthesis of methyl 2-hydrazinyl-6-chloronicotinate

To the mixed solution of 11.5 g (55.8 mmol) of methyl 2,6-dichloronicotinate and 150 ml of dioxane, 5.58 g (111 mmol) of hydrazine monohydrate was added at room temperature. After completion of the addition, the reaction mixture was stirred for 18 hours at room temperature. After completion of stirring, the reaction was terminated by adding water and the solvent in the reaction liquid was distilled away under reduced pressure. The precipitated solid was washed with water and filtered to give 10.7 g of the target product as a yellow solid.

Melting point: 82° C. to 83° C.

Step 2; Synthesis of methyl 2-(2-isobutyrylhydrazinyl)-6-chloronicotinate

To the mixed solution of 5.0 g (24.8 mmol) of methyl 2-hydrazinyl-6-chloronicotinate, 2.5 g (24.8 mmol) of triethylamine, and 20 ml of tetrahydrofuran, 2.64 g (24.8 mmol) of isobutyryl chloride was added under cooling with ice. After completion of the addition, the reaction mixture was stirred for 2 hours under cooling with ice. After completion of stirring, the reaction was terminated by adding water and the reaction liquid was extracted with ethyl acetate (150 ml, 1 time). The obtained organic phase was washed with water. Thereafter, the organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and then anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and hexane and filtered to give 5.90 g of the target product as a white solid.

Melting point: 147° C. to 148° C.

Step 3; Synthesis of methyl 3-isopropyl-5-chloro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

5.9 g (21.7 mmol) of methyl 2-(2-isobutyrylhydrazinyl)-6-chloronicotinate and 20 ml of phosphoryl chloride were mixed at room temperature and thereafter the reaction mixture was stirred for 5 hours under heating to reflux. After completion of stirring, the reaction mixture was added to ice-water to terminate the reaction. Thereafter, the reaction liquid was washed with ethyl acetate (50 ml, 1 time). Potassium carbonate was added to the obtained aqueous phase under cooling with ice to adjust the pH to 8 to 9 and the reaction liquid was extracted with ethyl acetate (200 ml, 2 times). The obtained organic phase was dried over anhydrous sodium sulfate and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 4.75 g of the target product as a brownish light yellow solid.

Melting point: 105° C. to 107° C.

Step 4; Synthesis of methyl 3-isopropyl-5-(methylthio)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

To the mixed solution of 420 mg (1.66 mmol) of methyl 3-isopropyl-5-chloro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate and 3 ml of N,N-dimethylformamide, 140 mg (1.99 mmol) of sodium thiomethoxide was added under cooling with ice. After completion of the addition, the reaction mixture was stirred for 45 minutes under cooling with ice. After completion of stirring, the reaction was terminated by adding water and the reaction liquid was extracted with ethyl acetate (30 ml, 3 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and then anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 280 mg of the target product as a brown solid.

Melting point: 142° C. to 145° C.

Step 5; Synthesis of 3-isopropyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(methylthio)-[1,2,4]triazolo[4,3-a]pyrid ine-8-carboxamide

To the mixed solution of 140 mg (0.53 mmol) of methyl 3-isopropyl-5-(methylthio)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate, 3 ml of methanol, and 1 ml of water, 0.6 ml of 1 M sodium hydroxide aqueous solution was added at room temperature. After completion of the addition, the reaction mixture was stirred for 17 hours at room temperature. After completion of stirring, the reaction was terminated by adding 1 ml of 1 M hydrochloric acid. The solvent in the reaction liquid was distilled away under reduced pressure to give crude 3-isopropyl-5-(methylthio)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid. To the mixed solution of 190 mg (0.53 mmol) of the obtained crude 3-isopropyl-5-(methylthio)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid, 104 mg (1.06 mmol) of 5-methyl-1,3,4-oxadiazol-2-amine, and 3 ml of pyridine, 126 mg (1.06 mmol) of thionyl chloride was added at room temperature. After completion of the addition, the reaction mixture was stirred at 60° C. for 5 hours. After completion of stirring, the reaction was terminated by adding water and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and chloroform and filtered to give 57 mg of the target product as an ocherous solid.

Synthesis Example 4 3-Chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide (Compound No. 1-013) Step 1; Synthesis of 3-chloro-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

To the mixed solution of 300 mg (1.30 mmol) of 5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid and 6 ml of N,N-dimethylformamide, 347 mg (2.60 mmol) of N-chlorosuccinimide was added at room temperature. After completion of the addition, the reaction mixture was stirred at 60° C. for 4 hours. After completion of stirring, the reaction was terminated by adding water and the reaction liquid was extracted with ethyl acetate (50 ml, 2 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and then anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 210 mg of the target product as a brown solid.

Step 2; Synthesis of 3-chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyri dine-8-carboxamide

To the mixed solution of 70 mg (0.26 mmol) of 3-chloro-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid, 52 mg (0.53 mmol) of 5-methyl-1,3,4-oxadiazol-2-amine, 10 mg (0.03 mmol) of 4-(dimethylamino)pyridine, and 5 ml of pyridine, 63 mg (0.53 mmol) of thionyl chloride was added at room temperature. The reaction mixture was stirred for 1 hour at room temperature. After completion of stirring, the reaction was terminated by adding water and the reaction liquid was extracted with chloroform (15 ml, 3 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and then anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 52 mg of the target product as a light yellow solid.

Melting point: 238° C. to 241° C.

Synthesis Example 5 3-Isopropyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4, 3-a]pyridine-8-carboxamide (Compound No. 3-001)

To the mixed solution of 165 mg (0.60 mmol) of 3-isopropyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid, 0.1 ml of N,N-dimethylformamide, and 5 ml of methylene chloride, 83 mg (0.66 mmol) of oxalyl chloride was added at room temperature. After completion of the addition, the reaction mixture was stirred for 20 minutes at room temperature. After completion of stirring, the mixed solution of 119 mg (1.21 mmol) of 4-methyl-1,2,5-oxadiazol-3-amine, 122 mg (1.21 mmol) of triethylamine, and 3 ml of methylene chloride was added. After completion of the addition, the reaction mixture was stirred for 1 hour at room temperature. After completion of stirring, the solvent was distilled away under reduced pressure. The obtained residue was purified with silica gel chromatography (n-hexane:ethyl acetate=9:1 to 2:1) to give 168 mg of the target product as a white solid.

Melting point: 185° C. to 186° C.

Synthesis Example 6 5-Chloro-3-isopropyl-N-(1-methyl-1H-tetrazol-5-yl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide (Compound No. 2-004)

To the mixed solution of 500 mg (1.97 mmol) of methyl 5-chloro-3-isopropyl-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate, 3 ml of methanol, and 1 ml of water, 2 ml of 1 M sodium hydroxide aqueous solution was added under cooling with ice. After completion of the addition, the reaction mixture was stirred for 1 hour at room temperature. After completion of stirring, the reaction was terminated by adding 2.5 ml of 1 M hydrochloric acid. The solvent in the reaction liquid was distilled away under reduced pressure to give crude 5-chloro-3-isopropyl-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid. To the mixed solution of 500 mg (1.97 mmol) of the obtained crude 5-chloro-3-isopropyl-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid, 390 mg (3.94 mmol) of 1-methyl-1H-tetrazol-5-amine, 24 mg (0.19 mmol) of 4-(dimethylamino)pyridine, and 5 ml of pyridine, 469 mg (3.94 mmol) of thionyl chloride was added at room temperature. After completion of the addition, the reaction mixture was stirred for 2 days at room temperature. After completion of stirring, the reaction was terminated by adding water and the reaction liquid was extracted with ethyl acetate (50 ml, 2 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and then anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The obtained residue was purified with silica gel chromatography (n-hexane:ethyl acetate=4:1 to 1:1) to give 140 mg of the target product as a light yellow solid.

Melting point: 189° C. to 190° C.

Synthesis Example 7 3-(Methoxymethyl)-N-(1-methyl-1H-tetrazol-5-yl)-5-(trifluoromethyl)-[1,2,4]triazol o[4,3-a]pyridine-8-carboxamide (Compound No. 2-010) Step 1; Synthesis of methyl 2-(2-(2-methoxyacetyl)hydrazinyl)-6-(trifluoromethyl)nicotinate (Compound No. A1-05a)

To the mixed solution of 1.0 g (4.25 mmol) of methyl 2-hydrazinyl-6-(trifluoromethyl)nicotinate, 473 mg (4.68 mmol) of triethylamine, and 20 ml of tetrahydrofuran, 2 ml of tetrahydrofuran solution of 508 mg (4.68 mmol) of methoxyacetyl chloride was added under cooling with ice. After completion of the addition, the reaction solution was stirred for 30 minutes under cooling with ice. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure. After 15 ml of water was added, the mixture was extracted with chloroform (30 ml, 1 time and 10 ml, 2 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and then anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 1.16 g of the target product as a white solid.

Melting point: 76° C. to 77° C.

Step 2; Synthesis of methyl 3-(methoxymethyl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate (Compound No. B1-05a)

To the mixed solution of 1.16 g (3.78 mmol) of methyl 2-(2-(2-methoxyacetyl)hydrazinyl)-6-(trifluoromethyl)nicotinate and 17 ml of toluene, 1.74 g (11.3 mmol) of phosphoryl chloride was added at room temperature. After completion of the addition, the reaction solution was stirred for 5 hours under heating to reflux. After completion of the reaction, the reaction solution was poured into separately prepared 20 ml of water. A sodium hydrogen carbonate aqueous solution was added to adjust the pH to 8 to 9 and thereafter the resultant mixture was extracted with ethyl acetate (30 ml, 1 time and 15 ml, 3 times). The combined organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and then anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 721 mg of the target product as a yellow solid.

Melting point: 95° C. to 97° C.

Step 3; Synthesis of 3-(methoxymethyl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid (Compound No. C1-05)

To the mixed solution of 693 mg (2.39 mmol) of methyl 3-(methoxymethyl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate and 7 ml of ethanol, 7 ml of aqueous solution of 115 mg (2.87 mmol) of sodium hydroxide was added under cooling with ice. After completion of the addition, the reaction solution was stirred for 30 minutes under cooling with ice. After completion of the reaction, 1 M hydrochloric acid was added to the reaction solution to adjust the pH to 2 to 3. Thereafter, the resultant mixture was extracted with chloroform (30 ml, 1 time and 15 ml, 3 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 553 mg of the target product as a yellow solid.

Melting point: 111° C. to 112° C.

Step 4; Synthesis of 3-(methoxymethyl)-N-(1-methyl-1H-tetrazol-5-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide

To the mixed solution of 100 mg (0.36 mmol) of 3-(methoxymethyl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid, 72 mg (0.73 mmol) of 1-methyl-1H-tetrazol-5-amine, 5 mg of 4-dimethylaminopyridine, and 2 ml of pyridine, 87 mg (0.73 mmol) of thionyl chloride was added at room temperature. After completion of the addition, the reaction solution was stirred at room temperature for 30 minutes. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure. To the obtained residue, 1 mol/L hydrochloric acid was added to adjust the pH to 2 to 3. Thereafter, the resultant mixture was extracted with chloroform (15 ml, 3 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 76 mg of the target product as a white solid.

Melting point: 205° C. to 209° C.

Synthesis Example 8 N-(5-Methyl-1,3,4-oxadiazol-2-yl)-3-(methylthio)-5-(trifluoromethyl)-[1,2,4]triazol o[4,3-a]pyridine-8-carboxamide (Compound No. 1-018) Step 1; Synthesis of methyl 3-thioxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

The mixed solution of 1.0 g (4.25 mmol) of methyl 2-hydrazinyl-6-(trifluoromethyl)nicotinate, 795 mg (4.46 mmol) of 1,1′-thiocarbonyldiimidazole, and 10 ml of N,N-dimethylformamide was stirred at 60° C. for 3 hours. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 534 mg of the mixture of the target product and imidazole as a red solid.

Step 2; Synthesis of methyl 3-(methylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

To 10 ml of N,N-dimethylformamide solution of 534 mg of methyl 3-thioxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate obtained in Step 1 containing imidazole, 402 mg of methyl iodide was added at room temperature. After completion of the addition, the reaction solution was stirred at room temperature for 1.5 hours. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure. 15 ml of water was added to the obtained residue and the resultant mixture was extracted with chloroform (15 ml, 3 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 336 mg of the target product as a yellow solid.

Melting point: 163° C. to 167° C.

Step 3; Synthesis of 3-(methylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

To the mixed solution of 332 mg (1.14 mmol) of methyl 3-(methylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate and 3 ml of methanol, 2.8 ml (1.4 mmol) of 0.5 mol/L sodium hydroxide aqueous solution was added under cooling with ice. After completion of the addition, the reaction solution was stirred for 1 hour under cooling with ice. After completion of the reaction, 1 mol/L hydrochloric acid was added to the reaction solution to adjust the pH to 2 to 3. The precipitated solid was washed with 1 mol/L hydrochloric acid, water, and diisopropyl ether and filtered to give 228 mg of the target product as a yellow solid.

Melting point: 158° C. to 162° C.

Step 4; Synthesis of N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-(methylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide

To the mixed solution of 100 mg (0.36 mmol) of 3-(methylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid, 71 mg (0.72 mmol) of 5-methyl-1,3,4-oxadiazol-2-amine, 4 mg of 4-dimethylaminopyridine, and 2 ml of pyridine, 129 mg (1.08 mmol) of thionyl chloride was added under cooling with ice. After completion of the addition, the reaction solution was stirred at room temperature for 20 minutes. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure. To the obtained residue, 1 mol/L hydrochloric acid was added to adjust the pH to 2 to 3. Thereafter, the resultant mixture was extracted with chloroform (15 ml, 3 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 100 mg of the target product as a yellow solid.

Melting point: 230° C. to 233° C.

Synthesis Example 9 3-Isopropyl-N-(1-methyl-1H-tetrazol-5-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carbothioamide (compound No. 2-039)

The mixed solution of 100 mg (0.28 mmol) of 3-isopropyl-N-(1-methyl-1H-tetrazol-5-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyrid ine-8-carboxamide, 114 mg (0.28 mmol) of Lawesson's reagent [2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide], and 3 ml of toluene was stirred at 110° C. for 5 hours. After completion of stirring, 114 mg (0.28 mmol) of Lawesson's reagent was added to the reaction solution and the resultant solution was additionally stirred at 110° C. for 3 hours. After completion of the reaction, 5 ml of 0.1 N hydrochloric acid was added to the reaction solution and the resultant mixture was extracted with ethyl acetate (15 ml, 1 time). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The obtained residue was purified with the medium pressure preparative liquid chromatography eluting the residue with n-hexane-ethyl acetate (gradient from 4:1 to 3:7) to give 66 mg of the target product as a yellow solid.

Melting point: 198° C. to 200° C.

Synthesis Example 10 3-Allyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide and N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide (compound No. 1-159 and compound No. 1-159*) Step 1; Synthesis of methyl 3-allyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate and methyl 3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

To the mixed solution of 1.20 g (3.96 mmol) of methyl 2-(2-(but-3-enoyl)hydrazinyl)-6-(trifluoromethyl)nicotinate synthesized in a similar method to the Step 1 in Synthesis Example 7 and 18 ml of toluene, 1.82 g (11.9 mmol) of phosphoryl chloride was added at room temperature. After completion of the addition, the reaction solution was stirred for 5 hours under heating to reflux. After completion of the reaction, the reaction solution was poured into separately prepared 20 ml of water. A sodium hydrogen carbonate aqueous solution was added to adjust the pH to 8 to 9 and thereafter the resultant mixture was extracted with ethyl acetate (30 ml, 1 time and 15 ml, 3 times). The combined organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and then anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The obtained residue was purified with the medium pressure preparative liquid chromatography eluting the residue with n-hexane-ethyl acetate (gradient from 7:3 to 0:1) to give 730 mg of the target product as a white solid [methyl 3-allyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate/methyl 3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate=4/1].

¹H NMR of methyl 3-allyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate (CDCl₃, Me₄Si, 300 MHz) δ 7.97 (d, 1H, J=7.2 Hz), 7.44 (d, 1H, J=7.2 Hz), 6.31-6.20 (m, 1H), 5.26-5.12 (m, 2H), 4.10 (s, 3H), 4.00 (dd, 2H, J=6.3 Hz, 1.2 Hz).

¹H NMR of methyl 3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate (CDCl₃, Me₄Si, 300 MHz) δ 7.94 (d, 1H, J=6.0 Hz), 7.42 (d, 1H, J=6.0 Hz), 7.00-6.90 (m, 1H), 6.66-6.58 (m, 1H), 4.10 (s, 3H), 2.04 (dd, 3H, J=6.6 Hz, 1.8 Hz).

Melting point: 121° C. to 123° C.

Step 2; Synthesis of 3-allyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid and 3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

To the mixed solution of 720 mg (2.65 mmol) of the mixture of methyl 3-allyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate and methyl 3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate and 10 ml of ethanol, 7.0 ml (3.5 mmol) of 0.5 mol/L sodium hydroxide aqueous solution was added under cooling with ice. After completion of the addition, the reaction solution was stirred for 30 minutes under cooling with ice. After completion of the reaction, 1 M hydrochloric acid was added to the reaction solution to adjust the pH to 2 to 3. Thereafter, the resultant mixture was extracted with ethyl acetate (15 ml, 2 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure to give 467 mg of the target product as a white solid [3-allyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid/3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid=4/1].

¹H NMR of 3-allyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid (CDCl₃, Me₄Si, 300 MHz) δ 8.25 (d, 1H, J=7.5 Hz), 7.61 (d, 1H, 7.5 Hz), 6.34-6.20 (m, 1H), 5.35-5.22 (m, 2H), 4.00 (dd, 2H, J=6.3 Hz, 1.2 Hz). (The proton peak of CO₂H was not observed.)

¹H NMR of 3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid (CDCl₃, Me₄Si, 300 MHz) δ 8.22 (d, 1H, J=8.1 Hz), 7.58 (d, 1H, J=8.1 Hz), 7.12-7.00 (m, 1H), 6.67-6.60 (m, 1H), 2.07 (dd, 3H, J=6.9 Hz, 1.8 Hz). (The proton peak of CO₂H was not observed.)

Melting point: 103° C. to 104° C.

Step 3; Synthesis of 3-allyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide and N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide

To the mixed solution of 100 mg (0.37 mmol) of the mixture of 3-allyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid and 3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid, 55 mg (0.55 mmol) of 5-methyl-1,3,4-oxadiazol-2-amine, 5 mg (0.04 mmol) of 1-hydroxy-7-azabenzotriazole and 2 ml of N,N-dimethylformamide, 106 mg (0.55 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride was added at room temperature. After completion of the addition, the reaction mixture was stirred for 1 hour at room temperature. After completion of stirring, 3 ml of 1 mol/l hydrochloric acid was added and the reaction liquid was extracted with ethyl acetate (10 ml, 2 times). The obtained organic phase was washed with water. Thereafter, the organic phase was dried over anhydrous sodium sulfate and the solvent was distilled away under reduced pressure. The obtained solid was purified by recrystallization from ethyl acetate to give 67 mg of the target product as a light yellow solid. [3-allyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide/N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide=4/1].

¹H NMR of 3-allyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide (CDCl₃, Me₄Si, 300 MHz) δ 12.9 (brs, 1H), 8.42 (d, 1H, J=7.5 Hz), 7.63 (d, 1H, J=7.5 Hz), 6.38-6.24 (m, 1H), 5.36-5.23 (m, 2H), 4.03 (dd, 2H, J=6.9 Hz, 1.2 Hz), 2.59 (s, 3H).

¹H NMR of N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide (CDCl₃, Me₄Si, 300 MHz) δ 12.9 (brs, 1H), 8.38 (d, 1H, J=6.9 Hz), 7.60 (d, 1H, J=6.9 Hz), 7.12-7.00 (m, 1H), 6.69-6.62 (m, 1H), 2.60 (s, 3H), 2.09 (dd, 3H, J=6.6 Hz, 1.8 Hz).

Melting point: 159° C. to 161° C.

Synthesis Example 11 3-Allyl-N-(1-methyl-1H-tetrazol-5-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyri dine-8-carboxamide and N-(1-methyl-1H-tetrazol-5-yl)-3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1, 2,4]triazolo[4,3-a]pyridine-8-carboxamide (Compound No. 2-105 and compound No. 2-105*)

To the mixed solution of 100 mg (0.37 mmol) of the mixture of 3-allyl-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid and 3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid synthesized in Step 2 of Synthesis Example 7, 56 mg (0.57 mmol) of 1-methyl-1H-tetrazol-5-amine, and 2 ml of pyridine, 66 mg (0.55 mmol) of thionyl chloride was added at a temperature of 15° C. or lower. After completion of the addition, the temperature of the reaction solution was retained at 15° C. or lower and stirred for 1.5 hours. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure. To the obtained residue, 1.5 ml of acetonitrile and 2 ml of 1 mol/L hydrochloric acid were added and the resultant mixture was extracted with ethyl acetate (10 ml, 2 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with ethyl acetate and filtered to give 27 mg of the target product as a light brown solid. [3-allyl-N-(1-methyl-1H-tetrazol-5-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide/N-(1-methyl-1H-tetrazol-5-yl)-3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1, 2,4]triazolo[4,3-a]pyridine-8-carboxamide=3/1].

¹H NMR of 3-allyl-N-(1-methyl-1H-tetrazol-5-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide (CDCl₃, Me₄Si, 300 MHz) δ 12.5 (brs, 1H), 8.40 (d, 1H, J=7.5 Hz), 7.65 (d, 1H, J=7.5 Hz), 6.37-6.24 (m, 1H), 5.37-5.24 (m, 2H), 4.13 (s, 3H), 4.06 (dd, 2H, J=6.6 Hz, 1.2 Hz).

¹H NMR of N-(1-methyl-1H-tetrazol-5-yl)-3-(prop-1-en-1-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide (CDCl₃, Me₄Si, 300 MHz) δ 12.5 (brs, 1H), 8.36 (d, 1H, J=7.2 Hz), 7.62 (d, 1H, J=7.2 Hz), 7.13-7.01 (m, 1H), 6.70-6.62 (m, 1H), 4.13 (s, 3H), 2.10 (dd, 3H, J=6.6 Hz, 1.5 Hz).

Melting point: 164° C. to 167° C.

Synthesis Example 12 3-(2,2-Dichloro-1-methylcyclopropyl)-N-ethyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide (compound No. 1-174)

To 1 ml of N,N-dimethylformamide solution of 67 mg of 3-(2,2-dichloro-1-methylcyclopropyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 31 mg of potassium carbonate and 48 mg of ethyl iodide were added at room temperature. After completion of the addition, the reaction mixture was stirred at 55° C. for 30 minutes. After completion of the reaction, 2 ml of water was added and the resultant mixture was extracted with ethyl acetate (3 ml, 2 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and anhydrous magnesium sulfate in this order and the solvent was distilled away under reduced pressure. The obtained residue was purified with the medium pressure preparative liquid chromatography eluting the residue with n-hexane-ethyl acetate (gradient from 2:1 to 0:1) to give 21 mg of the target product as a colorless resinous substance.

¹H NMR (CDCl₃, Me₄Si, 300 MHz) δ 7.72 (d, 1H, J=7.8 Hz), 7.53 (d, 1H, J=7.8 Hz), 4.15 (q, 2H, J=7.2 Hz), 2.78 (d, 1H, J=7.8 Hz), 2.38 (s, 3H), 1.83 (d, 1H, J=7.8 Hz), 1.80 (s, 3H), 1.43 (t, 3H, J=7.2 Hz).

The compound of the present invention can be synthesized in accordance with Synthesis Examples described above. Examples of the compounds of the present invention produced in similar methods to Synthesis Example 1 to Synthesis Example 9 are listed in Fourth Table to Tenth Table. The present invention, however, is not limited to these examples. In Tables, Me is methyl group. Similarly, Et is ethyl group, Pr is propyl group, Pen is pentyl group, Hex is hexyl group, Ph is phenyl group, Bn is benzyl group, i- is iso, c- is cyclo, and t- is tertiary.

The substituents of D-2, D-3a, D-4a, D-5, D-6a, D-7a, D-8a, D-9, D-9a, D-9b, D-10a, D-11, D-12, D-13a, D-14, D-15, D-16a, D-16m, D-17, D-17a, D-17b, D-18, D-19, D-20a, D-23a, and D-24f in Tables are the following structures.

In Tables, “*1” is “Resinous”. “*2” means that decomposition was observed at the time of melting point measurement. “*3” is a mixture of the compounds 1-158 and 1-158* of the present invention that are isomers having different structures and the ratio thereof 1-158/1-158* equals to 9/1. As described in Synthesis Example 10, “*4” is the mixture of the compounds 1-159 and 1-159* of the present invention that are isomers having different structures and the ratio thereof 1-159/1-159* equals to 4/1. As described in Synthesis Example 11, “*5” is the mixture of the compounds 2-105 and 2-105* of the present invention that are isomers having different structures and the ratio thereof 2-105/2-105* equals to 3/1.

FOURTH TABLE

TABLE 27 Melting point No. R^(1a) (R^(2a))_(n) X R³ R^(4a) (° C.) 1-001 H 5-CF₃ O H Me 220-223 1-002 Me 5-CF₃ O H Me 242-245 1-003 i-Pr 5-Me O H Me *2 1-004 i-Pr 5-CF₃ O H Me 176-178 1-005 i-Pr 5-CF₃ O H Et 176-180 1-006 i-Pr 5-CF₃ O H Bn 141-150 1-007 i-Pr 5-CF₃ O H Ph 173-177 1-008 i-Pr 5-CF₃ O H D-2 152-156 1-009 i-Pr 5-SMe O H Me *2 1-010 c-Pr 5-CF₃ O H Me 157-165 1-011 3-Pen 5-CF₃ O H Me 171-174 1-012 Ph 5-CF₃ O H Me 266-270 1-013 Cl 5-CF₃ O H Me 238-241 1-014 Br 5-CF₃ O H Me 252-260 1-015 CH₂OMe 5-CF₃ O H Me 115-125 1-016 4-MeO—Ph 5-CF₃ O H Me 205-208 1-017 4-Cl—Ph 5-CF₃ O H Me 256-258 1-018 SMe 5-CF₃ O H Me 230-233 1-019 CH₂O(CH₂)₂OMe 5-CF₃ O H Me 90-91 1-020 CH₂OCH₂CF₃ 5-CF₃ O H Me 148-149 1-021 CH(CH₃)CH₂CH₃ 5-CF₃ O H Me 160-162 1-022 D-3a 5-CF₃ O H Me 218-221 1-023 i-Pr 6-CF₃ O H Me 160-162 1-024 n-Pr 5-CF₃ O H Me 172-176 1-025 CH₂OPh 5-CF₃ O H Me 188-190 1-026 c-Pen 5-CF₃ O H Me 170-171 1-027 CH₂OEt 5-CF₃ O H Me 141-143 1-028 tBu 5-CF₃ O H Me 161-165 1-029 D-4a 5-CF₃ O H Me 172-176 1-030 CH₂SMe 5-CF₃ O H Me 153-155 1-031 CH₂SCH₂CF₃ 5-CF₃ O H Me 162-163 1-032 SEt 5-CF₃ O H Me 182-184 1-033 SCH(CH₃)₂ 5-CF₃ O H Me 186-188 1-034 S(O)Et 5-CF₃ O H Me 192-193 1-035 S(O)CH(CH₃)₂ 5-CF₃ O H Me 153-157 1-036 CH₂S(O)Me 5-CF₃ O H Me 190-191 1-037 CH₂S(O)₂Me 5-CF₃ O H Me *1 1-038 CH₂S(O)CH₂CF₃ 5-CF₃ O H Me 200-202 1-039 CH₂S(O)₂CH₂CF₃ 5-CF₃ O H Me *1 1-040 S(O)₂Me 5-CF₃ O H Me *1 1-041 S(O)₂Et 5-CF₃ O H Me *1 1-042 CH₂C(O)OEt 5-CF₃ O H Me 187-189 1-043 4-Me—Ph 5-CF₃ O H Me 221-223 1-044 4-F—Ph 5-CF₃ O H Me 203-208 1-045 4-CF₃—Ph 5-CF₃ O H Me 196-198 1-046 3-MeO—Ph 5-CF₃ O H Me 178-182 1-047 2-MeO—Ph 5-CF₃ O H Me 180-185 1-048 CH₂C(O)OH 5-CF₃ O H Me 139-141

TABLE 28 Melting point No. R^(1a) (R^(2a))_(n) X R³ R^(4a) (° C.) 1-049 CH₂C(O)OCH(CH₃)₂ 5-CF₃ O H Me 157-159 1-050 i-Pr 5-CF₃ O H H 171-175 1-051 i-Pr 5-CF₃ O H c-Pr 161-162 1-052 i-Pr 5-CF₃ O H (CH₂)₂OMe 125-135 1-053 i-Pr 5-CF₂H O H Me 160-162 1-054 D-8a 5-CF₃ O H Me 240-243 1-055 D-9a 5-CF₃ O H Me 205-208 1-056 D-10a 5-CF₃ O H Me 274-275 1-057 D-11 5-CF₃ O H Me 222-224 1-058 D-12 5-CF₃ O H Me 213-216 1-059 D-13a 5-CF₃ O H Me 272-274 1-060 CH₂C(O)O(CH₂)₂OMe 5-CF₃ O H Me 152-153 1-061 CH₂C(O)NHCH(CH₃)₂ 5-CF₃ O H Me 222-227 1-062 CH₂OC(O)Me 5-CF₃ O H Me 165-167 1-063 S(CH₂)₂OMe 5-CF₃ O H Me  99-101 1-064 SCH₂CH═CH₂ 5-CF₃ O H Me 213-217 1-065 SCH₂C≡CH 5-CF₃ O H Me 114-117 1-066 i-Pr 5-CF₂CF₃ O H Me 193-195 1-067 CH₂OH 5-CF₃ O H Me 236-238 1-068 CHO 5-CF₃ O H Me 222-223 1-069 CH₂(4-MeO—Ph) 5-CF₃ O H Me 172-174 1-070 3,5-(MeO)₂—Ph 5-CF₃ O H Me 228-229 1-071 3,5-(Cl)₂—Ph 5-CF₃ O H Me 254-256 1-072 CH═NOMe 5-CF₃ O H Me 204-207 1-073 S(O)(CH₂)₂OMe 5-CF₃ O H Me 199-201 1-074 S(O)CH₂CH═CH₂ 5-CF₃ O H Me 134-137 1-075 i-Pr 5-CF₃-6-Me O H Me 168-169 1-076 NMe₂ 5-CF₃ O H Me 184-185 1-077 S(O)CH₂C≡CH 5-CF₃ O H Me 205-212 1-078 CH(Me)SMe 5-CF₃ O H Me 137-139 1-079 CH(Me)S(O)Me 5-CF₃ O H Me 127-129 1-080 CH(Me)S(O)₂Me 5-CF₃ O H Me 159-160 1-081 i-Pr 5-Ph O H Me 131-133 1-082 NHPh 5-CF₃ O H Me 179-182 1-083 (CH₂)₂SMe 5-CF₃ O H Me 157-159 1-084 (CH₂)₂S(O)Me 5-CF₃ O H Me 179-181 1-085 (CH₂)₂S(O)₂Me 5-CF₃ O H Me 191-192 1-086 N(Me)Ph 5-CF₃ O H Me 175-178 1-087 S(CH₂)₂CH₃ 5-CF₃ O H Me 141-142 1-088 i-Pr 5-[3,5-(F)₂—Ph} O H Me 191-193 1-089 i-Pr 5-CF₃-7-Me O H Me 120-124 1-090 NHCH(CH₃)₂ 5-CF₃ O H Me 163-164 1-091 SCH(CH₃)₂ 5-CF₃ O H H 211-213 1-092 S(O)(CH₂)₂CH₃ 5-CF₃ O H Me 193-195 1-093 SCH₂CH(CH₃)₂ 5-CF₃ O H Me 143-145 1-094 SCH(CH₃)CH₂CH₃ 5-CF₃ O H Me 150-153 1-095 SC(CH₃)₃ 5-CF₃ O H Me 178-180 1-096 D-14 5-CF₃ O H Me 166-168

TABLE 29 Melting point No. R^(1a) (R^(2a))_(n) X R³ R^(4a) (° C.) 1-097 i-Pr 5-CF₃ O H D-15 108-111 1-098 i-Pr 5-CF₃ O H D-14 *1 1-099 i-Pr 5-CF₃ O H 4-MeO—Ph 154-158 1-100 i-Pr 5-CF₃ O H CF₃ 111-116 1-101 i-Pr 5-CF₃ O H D-9 167-169 1-102 NH(D-9b) 5-CF₃ O H Me 219-221 1-103 NMe₂ 5-CF₃ O H H 200-205 1-104 CH₂(c-Pr) 5-CF₃ O H Me 160-163 1-105 D-16a 5-CF₃ O H Me 232-235 1-106 SEt 5-CF₃ O H H 189-191 1-107 CH₂O(CH₂)₂OMe 5-CF₃ O H H 117-118 1-108 S(CH₂)₂CH₃ 5-CF₃ O H H 198-200 1-109 NH(CH₂)₂OMe 5-CF₃ O H Me 150-155 1-110 D-14 5-CF₃ O H H 180-182 1-111 NHS(O)₂Ph 5-CF₃ O H Me 259-261 1-112 OEt 5-CF₃ O H H 135-145 1-113 SCH₂Ph 5-CF₃ O H Me 187-190 1-114 SCH₂(4-MeO—Ph) 5-CF₃ O H Me 155-158 1-115 SCH₂(c-Pr) 5-CF₃ O H Me 135-137 1-116 SCH₂(D-15) 5-CF₃ O H Me 142-143 1-117 SCH₂CN 5-CF₃ O H Me 179-182 1-118 D-17 5-CF₃ O H Me *1 1-119 D-17a 5-CF₃ O H Me 250-255 1-120 D-17b 5-CF₃ O H Me 235-238 1-121 N(Me)(CH₂)₂OMe 5-CF₃ O H H 131-134 1-122 N(Me)CH(CH₃)₂ 5-CF₃ O H H 155-157 1-123 N(Me)(c-Hex) 5-CF₃ O H H 64-66 1-124 SCH₂CF₃ 5-CF₃ O H Me 156-157 1-125 SCH₂C(O)CH₃ 5-CF₃ O H Me 178-182 1-126 SCH₂(D-18) 5-CF₃ O H Me 200-203 1-127 SCH₂C(O)OMe 5-CF₃ O H Me 184-185 1-128 SCH₂CH═CH₂ 5-CF₃ O H H 188-190 1-129 N(Me)(CH₂)₂OMe 5-CF₃ O H Me 75-80 1-130 NH(CH₂)₂SMe 5-CF₃ O H Me 111-115 1-131 NHCH₂CF₃ 5-CF₃ O H Me 140-144 1-132 N(Me)CH(CH₃)₂ 5-CF₃ O H Me 164-168 1-133 N(Me)(c-Hex) 5-CF₃ O H Me 135-140 1-134 N(Me)Et 5-CF₃ O H Me 125-128 1-135 N(Et)₂ 5-CF₃ O H Me 135-137 1-136 D-19 5-CF₃ O H Me 151-152 1-137 N(Me)Et 5-CF₃ O H H 141-143 1-138 N(Et)₂ 5-CF₃ O H H 130-131 1-139 D-19 5-CF₃ O H H 217-218 1-140 i-Pr 5-CF₃ O H D-11 200-201 1-141 i-Pr 5-CF₃ O H CH₂SMe 114-116 1-142 i-Pr 5-CF₃ O H CH₂S(O)₂Me 171-173 1-143 i-Pr 5-CF₃ O H CH₂S(O)Me 149-150 1-144 c-Pr 5-CF₃ O H H 170-174

TABLE 30 Melting point No. R^(1a) (R^(2a))_(n) X R³ R^(4a) (° C.) 1-145 3-Pen 5-CF₃ O H H 228-231 1-146 CH₂SMe 5-CF₃ O H H 176-179 1-147 4-F—Ph 5-CF₃ O H H 222-226 1-148 3,5-(MeO)₂—Ph 5-CF₃ O H H 217-220 1-149 4-MeO—Ph 5-CF₃ O H H 210-213 1-150 D-8a 5-CF₃ O H H 244-248 1-151 CH₂(4-MeO—Ph) 5-CF₃ O H H 187-190 1-152 N(Me)CH₂C≡CH 5-CF₃ O H Me 161-163 1-153 N(Me)(CH₂)₂CN 5-CF₃ O H Me 138-143 1-154 S(c-Pen) 5-CF₃ O H Me 153-155 1-155 S(c-Pen) 5-CF₃ O H H 214-216 1-156 SCH₂(D-8a) 5-CF₃ O H Me 171-172 1-157 SCH₂(D-8a) 5-CF₃ O H H 204-207 1-158 CH₂CH═CH₂ 5-CF₃ O H H    155-158(*3) 1-158* CH═CHMe 5-CF₃ O H H    155-158(*3) 1-159 CH₂CH═CH₂ 5-CF₃ O H Me    159-161(*4) 1-159* CH═CHMe 5-CF₃ O H Me    159-161(*4) 1-160 C≡CMe 5-CF₃ O H H *2 1-161 C≡CMe 5-CF₃ O H Me >280 1-162 CH₂CF₃ 5-CF₃ O H Me 199-203 1-163 N(Me)CH₂C≡CH 5-CF₃ O H H 216-218 1-164 N(Me)(CH₂)₂CN 5-CF₃ O H H 105-110 1-165 N(Me)(4-MeO—Ph) 5-CF₃ O H Me 136-139 1-166 N(Me)CH₂CH═CH₂ 5-CF₃ O H Me 127-129 1-167 N(Me)CH₂(4-MeO—Ph) 5-CF₃ O H Me 191-194 1-168 CH₂CN 5-CF₃ O H Me 196-199 1-169 D-16m 5-CF₃ O H Me 146-147 1-170 D-24f 5-CF₃ O H Me 182-185 1-171 N(Me)(4-MeO—Ph) 5-CF₃ O H H 180-185 1-172 N(Me)CH₂CH═CH₂ 5-CF₃ O H H 135-137 1-173 (CH₂)₂OMe 5-CF₃ O H Me 157-158 1-174 D-16a 5-CF₃ O Et Me *1

FIFTH TABLE

TABLE 31 No. R^(1a) (R^(2a))_(n) X R³ R^(5a) Melting point (° C.) 2-001 H 5-CF₃ O H Me 247-251 2-002 Me 5-CF₃ O H Me 215-219 2-003 i-Pr 5-CF₃ O H Me 215-220 2-004 i-Pr 5-Cl O H Me 189-190 2-005 c-Pr 5-CF₃ O H Me 190-195 2-006 3-Pen 5-CF₃ O H Me 143-144 2-007 Ph 5-CF₃ O H Me 245-247 2-008 Cl 5-CF₃ O H Me 193-195 2-009 Br 5-CF₃ O H Me 186-193 2-010 CH₂OMe 5-CF₃ O H Me 205-209 2-011 4-MeO—Ph 5-CF₃ O H Me 173-177 2-012 4-Cl—Ph 5-CF₃ O H Me 256-258 2-013 SMe 5-CF₃ O H Me 210-215 2-014 CH₂O(CH₂)₂OMe 5-CF₃ O H Me 152-154 2-015 CH₂OCH₂CF₃ 5-CF₃ O H Me 170-171 2-016 CH(CH₃)CH₂CH₃ 5-CF₃ O H Me 181-184 2-017 D-3a 5-CF₃ O H Me 251-253 2-018 i-Pr 6-CF₃ O H Me 169-171 2-019 n-Pr 5-CF₃ O H Me 149-150 2-020 CH₂OPh 5-CF₃ O H Me 116-117 2-021 c-Pen 5-CF₃ O H Me 197-201 2-022 D-5 5-CF₃ O H Me 147-149 2-023 i-Pr 5-CF₃ O Me Me 215-216 2-024 SEt 5-CF₃ O H Me 157-159 2-025 SCH(CH₃)₂ 5-CF₃ O H Me 200-204 2-026 CH₂OEt 5-CF₃ O H Me 183-184 2-027 tBu 5-CF₃ O H Me 217-218 2-028 D-4a 5-CF₃ O H Me 186-188 2-029 CH₂SMe 5-CF₃ O H Me 189-191 2-030 CH₂SCH₂CF₃ 5-CF₃ O H Me 155-158 2-031 S(O)Et 5-CF₃ O H Me 190-191 2-032 S(O)CH(CH₃)₂ 5-CF₃ O H Me 163-167 2-033 CH₂S(O)Me 5-CF₃ O H Me 204-206 2-034 CH₂S(O)₂Me 5-CF₃ O H Me 212-214 2-035 CH₂S(O)CH₂CF₃ 5-CF₃ O H Me 138-142 2-036 CH₂S(O)₂CH₂CF₃ 5-CF₃ O H Me 176-178 2-037 S(O)₂Me 5-CF₃ O H Me *1 2-038 S(O)₂Et 5-CF₃ O H Me *1 2-039 i-Pr 5-CF₃ S H Me 198-200 2-040 CH₂C(O)OEt 5-CF₃ O H Me 202-204 2-041 i-Pr 5-CF₃ O H CH₂CH₂OMe *1 2-042 4-Me—Ph 5-CF₃ O H Me 221-225 2-043 4-F—Ph 5-CF₃ O H Me 236-240 2-044 3-MeO—Ph 5-CF₃ O H Me 210-212 2-045 2-MeO—Ph 5-CF₃ O H Me 150-153 2-046 i-Pr 5-CF₃ O H CH₂C(O)OMe 149-154 2-047 i-Pr 5-CF₂H O H Me 172-173 2-048 i-Pr 5-CF₃ O H CH₂CH₂SMe *1

TABLE 32 No. R^(1a) (R^(2a))_(n) X R³ R^(5a) Melting point (° C.) 2-049 i-Pr 5-CF₂CF₃ O H Me 240-241 2-050 i-Pr 5-CF₃-6-Me O H Me 208-209 2-051 NMe₂ 5-CF₃ O H Me 222-225 2-052 CH(Me)SMe 5-CF₃ O H Me 202-204 2-053 CH(Me)S(O)Me 5-CF₃ O H Me 150-152 2-054 CH(Me)S(O)₂Me 5-CF₃ O H Me 117-125 2-055 i-Pr 5-Ph O H Me 193-198 2-056 NHPh 5-CF₃ O H Me 255-260 2-057 (CH₂)₂SMe 5-CF₃ O H Me 144-146 2-058 (CH₂)₂S(O)Me 5-CF₃ O H Me  96-102 2-059 (CH₂)₂S(O)₂Me 5-CF₃ O H Me 173-175 2-060 D-8a 5-CF₃ O H Me 217-220 2-061 D-11 5-CF₃ O H Me 223-224 2-062 D-10a 5-CF₃ O H Me 246-248 2-063 3,5-(MeO)₂—Ph 5-CF₃ O H Me 197-199 2-064 3,5-(Cl)₂—Ph 5-CF₃ O H Me 269-271 2-065 CH₂(4-MeO—Ph) 5-CF₃ O H Me 167-168 2-066 NHCH(CH₃)₂ 5-CF₃ O H Me 104-107 2-067 S(O)Me 5-CF₃ O H Me 228-229 2-068 S(CH₂)₂CH₃ 5-CF₃ O H Me 136-138 2-069 S(O)(CH₂)₂CH₃ 5-CF₃ O H Me 155-157 2-070 S(O)₂(CH₂)₂CH₃ 5-CF₃ O H Me 203-205 2-071 SCH₂CH(CH₃)₂ 5-CF₃ O H Me 159-160 2-072 SCH(CH₃)CH₂CH₃ 5-CF₃ O H Me 170-173 2-073 i-Pr 5-CF₃ O H Ph 133-136 2-074 NH(CH₂)₂OMe 5-CF₃ O H Me 111-115 2-075 D-14 5-CF₃ O H Me 240-245 2-076 SCH₂Ph 5-CF₃ O H Me 179-181 2-077 SCH₂(4-MeO—Ph) 5-CF₃ O H Me 190-192 2-078 D-17 5-CF₃ O H Me 285-290 2-079 N(Me)(CH₂)₂OMe 5-CF₃ O H Me 168-169 2-080 NH(CH₂)₂SMe 5-CF₃ O H Me *1 2-081 NHCH₂CF₃ 5-CF₃ O H Me *1 2-082 N(Me)CH(CH₃)₂ 5-CF₃ O H Me 171-172 2-083 N(Me)(c-Hex) 5-CF₃ O H Me 144-145 2-084 SCH₂(c-Pr) 5-CF₃ O H Me 168-169 2-085 SCH₂(D-15) 5-CF₃ O H Me 139-141 2-086 SCH₂CN 5-CF₃ O H Me 144-145 2-087 SCH₂CF₃ 5-CF₃ O H Me 160-161 2-088 N(Me)Et 5-CF₃ O H Me 110-112 2-089 N(Et)₂ 5-CF₃ O H Me 159-160 2-090 i-Pr 5-CF₃ O H n-Pr 111-112 2-091 i-Pr 5-CF₃ O H CH₂CH═CH₂ 118-119 2-092 i-Pr 5-CF₃ O H CH₂C(O)OEt 104-105 2-093 i-Pr 5-CF₃ O H CH₂(4-Cl—Ph) 147-148 2-094 N(Me)CH₂C≡CH 5-CF₃ O H Me 176-178 2-095 N(Me)(CH₂)₂CN 5-CF₃ O H Me 125-128 2-096 S(c-Pen) 5-CF₃ O H Me 192-194

TABLE 33 No. R^(1a) (R^(2a))_(n) X R³ R^(5a) Melting point (° C.) 2-097 SCH₂(D-8a) 5-CF₃ O H Me 175-178 2-098 SEt 5-CF₃ O H CH₂CH₂OMe 130-131 2-099 N(Me)(4-MeO—Ph) 5-CF₃ O H Me 141-142 2-100 N(Me)CH₂CH═CH₂ 5-CF₃ O H Me 183-184 2-101 S(CH₂)₂OMe 5-CF₃ O H Me 144-145 2-102 SCH₂CH═CH₂ 5-CF₃ O H Me 172-174 2-103 SCH₂C≡CH 5-CF₃ O H Me 190-191 2-104 i-Pr 5-CF₃ O H H 276-280 2-105 CH₂CH═CH₂ 5-CF₃ O H Me   164-167 (*5)  2-105* CH═CHMe 5-CF₃ O H Me   164-167 (*5) 2-106 C≡CMe 5-CF₃ O H Me 244-246 2-107 CH₂OC(O)Me 5-CF₃ O H Me 176-178 2-108 CH₂OH 5-CF₃ O H Me 155-158 2-109 CHO 5-CF₃ O H Me 250-252 2-110 D-16a 5-CF₃ O H Me 194-201

SIXTH TABLE

TABLE 34 No. R^(1a) (R^(2a))_(n) X R³ R^(4b) Melting point (° C.) 3-001 i-Pr 5-CF₃ O H Me 185-186 3-002 SCH₂CH(CH₃)₂ 5-CF₃ O H Me 136-137

SEVENTH TABLE

TABLE 35 No. R^(1a) (R^(2a))_(n) X R³ R^(4c) R^(5b) Melting point (° C.) 4-001 i-Pr 5-CF₃ O H H Me 182-185 4-002 i-Pr 5-CF₃ O H H Et *1 4-003 SEt 5-CF₃ O H H Me 119-120 4-004 i-Pr 5-CF₃ O H H H 250-255

EIGHTH TABLE

TABLE 36 Melting point No. R^(1a) (R^(2a))_(n) X R³ R^(4d) R^(5c) (° C.) 5-001 i-Pr 5-CF₃ O H Me Me 215-220 5-002 i-Pr 5-CF₃ O H —CH═CH—CH═CH— 219-223 5-003 i-Pr 5-CF₃ O H —(CH₂)₄— 130-135

NINTH TABLE

TABLE 37 No. Q R^(1b) (R^(2a))_(n) X R³ Melting point (° C.) 6-001 D-6a Me 5-CF₃ O H 250-260 6-002 D-7a Me 5-CF₃ O H 245-246 6-003 D-6a Et 5-CF₃ O H 234-236 6-004 D-7a Et 5-CF₃ O H 176-178 6-005 D-6a i-Pr 5-CF₃ O H 184-190 6-006 D-6a CH₂Ph 5-CF₃ O H 155-162 6-007 D-20a Et 5-CF₃ O H 182-185 6-008 D-23a Et 5-CF₃ O H 162-164

TENTH TABLE

TABLE 38 No. Q R^(1c) (R^(2c))_(n) X R³ Melting point (° C.) 7-001 D-6a i-Pr 5-CF₃ O H 252-255 7-002 D-7a i-Pr 5-CF₃ O H 168-170

Among the compounds of the present invention, ¹H-NMR data of compounds that have no melting points and the isomer mixtures of “*3”, “*4”, and “*5” are listed in Eleventh Table.

The chemical shift values of proton nuclear magnetic resonance were measured in a deuterated chloroform solvent at 300 MHz using Me₄Si (tetramethylsilane) as a reference substance. Symbols in Fourth Table have the following meanings. s: singlet, brs: broad-singlet, d: doublet, dd: double doublet, t: triplet, q: quartet, and m: multiplet.

[Eleventh Table]

TABLE 39 No. ¹H-NMR (CDCl₃, Me₄Si, 300 MHz) 1-003 δ8.21 (d, 1H, J = 7.2 Hz), 6.77 (d, 1H, J = 7.2 Hz), 3.85-3.70 (m, 1H), 2.97 (s, 3H), 2.55 (s, 3H), 1.58 (d, 6H, J = 7. 2 Hz)∘ 1-009 δ8.24 (d, 1H, J = 7.5 Hz), 6.67 (d, 1H, J = 7.5 Hz), 4.92 (brs, 1H), 4.25-4.10 (m, 1H), 2.75 (s, 3H), 2.55 (s, 3H), 1.60 (d, 6H, J = 6.9 Hz)∘ 1-037 δ8.51 (d, 1H, J = 6.9 Hz), 7.72 (d, 1H, J = 6.9 Hz), 5.05 (s, 2H), 3.26 (s, 3H), 2.60 (s, 3H)∘ (Proton peak of CONH was not observed.) 1-039 δ8.54 (d, 1H, J = 7.5 Hz), 7.76 (d, 1H, J = 7.5 Hz), 5.17 (s, 2H), 4.36 (q, 2H, J = 9.0 Hz), 2.60 (Proton peak of CONH was not observed.) 1-040 δ8.54 (d, 1H, J = 7.2 Hz), 7.79 (d, 1H, J = 7.2 Hz), 3.78 (s, 3H), 2.60 (s, 3H)∘ (Proton peak of CONH was not observed.) 1-041 δ8.53 (d, 1H, J = 7.5 Hz), 7.78 (d, 1H, J = 7.5 Hz), 4.00 (q, 2H, J = 7. 5 Hz), 2.60 (s, 3H), 1.59(t, 3H, J = 7.5 Hz)∘ (Proton peak of CONH was not observed.) 1-098 δ8.34 (d, 1H, J = 7.5 Hz), 7.59 (d, 1H, J = 7.5 Hz), 3.82 (t, 4H, J = 4.9 Hz), 3.79-3.68 (m, 1H), 3.54 (t, 4H, J = 4.9 Hz), 1.56(d, 6H, J = 6.5 Hz)∘ (Proton peak of CONH was not observed.) 1-118 δ12.68 (brs, 1H), 8.39 (d, 1H, J = 7.4 Hz), 7.59 (d, 1H, J = 7.4 Hz), 3.59-3.39 (m, 4H), 3.05-2.78 (m, 4H), 2.59 (s, 3H)∘ 1-158 δ13.1 (brs, 1H), 8.44 (d, 1H, J = 7.5 Hz), 8.30 (s, 1H), 7.64 (d, 1H, J = 7.5 Hz), 6.38-6.25 (m, 1H), 5.38-5.24 (m, 2H), 4.04 (dd, 2H, J = 3.9 Hz, 1.2 Hz)∘ 1-158* δ13.0 (brs, 1H), 8.43 (d, 1H, J = 6.6 Hz), 8.30 (s, 1H), 7.62 (d, 1H, J = 6.6 Hz), 7.11-7.01 (m, 1H), 6.71-6.61(m, 1H), 2.10 (d, 3H, J = 6.6 Hz)∘ 1-159 δ12.9 (brs, 1H), 8.42 (d, 1H, J = 7.5 Hz), 7.63 (d, 1H, J = 7.5 Hz), 6.38-6.24 (m, 1H), 5.36-5.23 (m, 2H), 4.03 (dd, 2H, J = 6.9 Hz, 1.2 Hz), 2.59 (s, 3H)∘ 1-159* δ12.9 (brs, 1H), 8.38 (d, 1H, J = 6.9 Hz), 7.60 (d, 1H, J = 6.9 Hz), 7.12-7.00 (m, 1H), 6.69-6.62 (m, 1H), 2.60 (s, 3H), 2.09 (dd, 3H, J = 6.6 Hz, 1.8 Hz)∘ 1-160 δ12.8 (brs, 1H), 8.46 (d, 1H, J = 7.2 Hz), 8.31 (s, 1H), 7.65 (d, 1H, J = 7.2 Hz), 2.27 (s, 3H)∘ 1-161 δ12.6 (brs, 1H), 8.44 (d, 1H, J = 7.2 Hz), 7.64 (d, 1H, J = 7.2 Hz), 2.59 (s, 3H), 2.27 (s, 3H)∘ 1-174 δ7.72 (d, 1H, J = 7.8 Hz), 7.53 (d, 1H, J = 7.8 Hz), 4.15 (q, 2H, J = 7.2 Hz), 2.78 (d, 1H, J = 7.8 Hz), 2.38 (s, 3H), 1.83 (d, 1H, J = 7.8 Hz), 1.80 (s, 3H), 1.43 (t, 3H, J = 7.2 Hz)∘ 2-037 δ12.08 (brs, 1H), 8.62 (d, 1H, J = 7.5 Hz), 7.86 (d, 1H, J = 7.5 Hz), 4.12 (s, 3H), 3.80 (s, 3H)∘ 2-038 δ12.11 (brs, 1H), 8.62 (d, 1H, J = 7.2 Hz), 7.86 (d, 1H, J = 7.2 Hz), 4.12 (s, 3H), 4.01 (q, 2H, J = 7.2 Hz), 1.60 (t, 3H, J = 7.2 Hz)∘ 2-041 δ12.49 (brs, 1H), 8.35 (d, 1H, J = 7.5 Hz), 7.62 (d, 1H, 7.5 Hz), 4.65-4.55 (m, 2H), 3.90-3.80 (m, 2H), 3.75-3.65 (m, 1H), 3.38 (s, 3H), 1.60-1.50(m, 6H)∘

TABLE 40 No. ¹H-NMR (CDCl₃, Me₄Si, 300 MHz) 2-048 δ12.6 (brs, 1H), 8.35 (d, 1H, J = 7.5 Hz), 7.64 (d, 1H, J = 7.5 Hz), 4.60 (t, 2H, J = 7.2 Hz), 3.80-3.65 (m, 1H), 3.09 (t, 2H, J = 7.2 Hz), 2.11 (s, 3H), 1.56 (d, 6H, J = 6.9 Hz)∘ 2-080 δ12.4 (brs, 1H), 8.14 (d, 1H, J = 6.6 Hz), 7.40 (d, 1H, J = 6.6 Hz), 5.24 (brs, 1H), 4.11 (s, 3H), 3.88-3.80 (m, 2H), 2.99-2.91 (m, 2H), 2.16 (s, 3H)∘ 2-081 δ12.3 (brs, 1H), 8.23 (d, 1H, J = 7.2 Hz), 7.49 (d, 1H, J = 7.2 Hz), 4.78 (brs, 1H), 4.45-4.32 (m, 2H), 4.11 (s, 3H)∘ 2-105 δ12.5 (brs, 1H), 8.40 (d, 1H, J = 7.5 Hz), 7.65 (d, 1H, J = 7.5 Hz), 6.37-6.24 (m, 1H), 5.37-5.24 (m, 2H), 4.13 (s, 3H), 4.06 (dd, 2H, J = 6.6 Hz, 1.2 Hz)∘ 2-105* δ12.5 (brs, 1H), 8.36 (d, 1H, J = 7.2 Hz), 7.62 (d, 1H, J = 7.2 Hz), 7.13-7.01 (m, 1H), 6.70-6.62 (m, 1H), 4.13 (s, 3H), 2.10 (dd, 3H, J = 6.6 Hz, 1.5 Hz)∘ 4-002 δ12.3(brs, 1H), 8.37 (d, 1H, J = 7.5 Hz), 7.88(s, 1H), 7.61 (d, 1H, J = 7.5 Hz), 4.23 (q, 2H, J = 7.5 Hz), 3.80-3.60 (m, 1H), 1.60-1.50 (m, 9H)∘

REFERENCE EXAMPLE Reference Example 1

Compounds listed in Twelfth Table were synthesized by a similar method to Step 1 of Synthesis Example 7. In Tables, Me is methyl group. Similarly, Et is ethyl group, Pr is propyl group, Pen is pentyl group, Ph is phenyl group, Bn is benzyl group, n- is normal, i- is iso, c- is cyclo, and t- is tertiary.

In Tables, substituents of D-3a, D-4a, D-5, D-8a, D-9a, D-10a, D-11, D-12, D-13a, D-14, D-16a, and D-16m are the following structures.

In Tables, “*1” is “Resinous”. ¹H-NMR data of compounds that have no melting points are listed in Sixteenth Table. The chemical shift values of proton nuclear magnetic resonance in Sixteenth Table were measured in a deuterated chloroform solvent at 300 MHz using Me₄Si (tetramethylsilane) as a reference substance. Symbols in Sixteenth Table have the following meanings. s: singlet, brs: broad-singlet, d: doublet, dd: double doublet, t: triplet, q: quartet, and m: multiplet.

TWELFTH TABLE

TABLE 41 Melting No. R¹ ^(a) (R^(2a))n Z¹ point (° C.) A1-01a H 6-CF₃ Me *1 A1-02a c-Pr 6-CF₃ Me 143-144 A1-03a 3-Pen 6-CF₃ Me 125-126 A1-04a Ph 6-CF₃ Me *1 A1-05a CH₂OMe 6-CF₃ Me 76-77 A1-06a 4-MeO—Ph 6-CF₃ Me 116-120 A1-07a 4-Cl—Ph 6-CF₃ Me 163-165 A1-08a CH₂O(CH₂)₂OMe 6-CF₃ Me *1 A1-09a CH₂OCH₂CF₃ 6-CF₃ Me 82-85 A1-10a CH(CH₃)CH₂CH₃ 6-CF₃ Me 148-149 A1-11a D-3a 6-CF₃ Me 121-122 A1-12a i-Pr 5-CF₃ Me 130-131 A1-13a n-Pr 6-CF₃ Me 119-120 A1-14a CH₂OPh 6-CF₃ Me 95-97 A1-15a c-Pen 6-CF₃ Me 158-159 A1-16a D-5 6-CF₃ Me 155-156 A1-17a CH₂OEt 6-CF₃ Me 55-57 A1-18a t-Bu 6-CF₃ Me 144-146 A1-19a D-4a 6-CF₃ Me  99-100 A1-20a CH₂SMe 6-CF₃ Me 127-129 A1-21a CH₂SCH₂CF₃ 6-CF₃ Me 114-116 A1-22b CH₂C(O)OEt 6-CF₃ Bn 110-112 A1-23a 4-Me—Ph 6-CF₃ Me 183-185 A1-24a 4-F—Ph 6-CF₃ Me 117-119 A1-25a 4-CF₃—Ph 6-CF₃ Me 160-162 A1-26a 3-MeO—Ph 6-CF₃ Me 103-106 A1-27a 2-MeO—Ph 6-CF₃ Me 160-164 A1-28a i-Pr 6-CF₂H Me 140-141 A1-29a D-8a 6-CF₃ Me 172-175 A1-30a D-9a 6-CF₃ Me 160-170 A1-31a D-10a 6-CF₃ Me 161-163 A1-32a D-11 6-CF₃ Me 45-50 A1-33a D-12 6-CF₃ Me 40-45 A1-34a D-13a 6-CF₃ Me 183-184 A1-35b CH₂OC(O)Me 6-CF₃ Bn 89-91 A1-36a CH₂(4-MeO—Ph) 6-CF₃ Me 121-122 A1-37c i-Pr 6-CF₂CF₃ Et 120-121 A1-38a 3,5-(MeO)₂—Ph 6-CF₃ Me 106-107 A1-39a 3,5-(Cl)₂—Ph 6-CF₃ Me 178-179 A1-40a i-Pr 5-Me-6-CF₃ Me 169-174 A1-41c i-Pr 4-Me-6-CF₃ Et 140-141 A1-42a (CH₂)₂SMe 6-CF₃ Me 90-91 A1-43a CH(Me)SMe 6-CF₃ Me 166-167 A1-44c i-Pr 6-Ph Et 144-146 A1-45c i-Pr 6-{3,5-(F)₂—Ph} Et 144-146 A1-46a NMe₂ 6-CF₃ Me 134-137 A1-47c D-14 6-CF₃ Et 101-105 A1-48a CH₂(c-Pr) 6-CF₃ Me 119-122

TABLE 42 Melting No. R¹ ^(a) (R^(2a))n Z¹ point (° C.) A1-49a D-16a 6-CF₃ Me 70-75 A1-50a C≡CMe 6-CF₃ Me 151-153 A1-51a CH₂CF₃ 6-CF₃ Me 170-172 A1-52a CH₂CN 6-CF₃ Me 163-165 A1-53c D-16m 6-CF₃ Et 120-125 A1-55c (CH₂)₂OMe 6-CF₃ Et 96-98

Reference Example 2

Compounds listed in Thirteenth Table were synthesized by a similar method to Step 2 of Synthesis Example 7. In Tables, Me is methyl group. Similarly, Et is ethyl group, Pr is propyl group, Pen is pentyl group, Ph is phenyl group, Bn is benzyl group, n- is normal, i- is iso, c- is cyclo, and t- is tertiary.

In Tables, substituents of D-3a, D-4a, D-5, D-8a, D-9a, D-10a, D-11, D-12, D-13a, D-14, D-16a, D-16m and D-24f are the following structures.

In Tables, “1” is “Resinous”. ¹H-NMR data of compounds that have no melting points are listed in Sixteenth Table.

THIRTEENTH TABLE

TABLE 43 Melting No. R^(1 a) (R^(2a))n Z¹ point (° C.) B1-01a H 5-CF₃ Me *1 B1-02a c-Pr 5-CF₃ Me *1 B1-04a Ph 5-CF₃ Me *1 B1-05a CH₂OMe 5-CF₃ Me 95-97 B1-06a 4-MeO—Ph 5-CF₃ Me 160-162 B1-07a 4-Cl—Ph 5-CF₃ Me 148-152 B1-08a CH₂O(CH₂)₂OMe 5-CF₃ Me *1 B1-09a CH₂OCH₂CF₃ 5-CF₃ Me 87-89 B1-10a CH(CH₃)CH₂CH₃ 5-CF₃ Me 86-94 B1-11a D-3a 5-CF₃ Me 140-141 B1-12a i-Pr 6-CF₃ Me 105-107 B1-13a n-Pr 5-CF₃ Me 129-130 B1-14a CH₂OPh 5-CF₃ Me 102-103 B1-15a c-Pen 5-CF₃ Me 130-134 B1-17a CH₂OEt 5-CF₃ Me 87-89 B1-18a t-Bu 5-CF₃ Me 75-77 B1-19a D-4a 5-CF₃ Me 137-139 B1-20a CH₂SMe 5-CF₃ Me 97-99 B1-21a CH₂SCH₂CF₃ 5-CF₃ Me 125-126 B1-22b CH₂C(O)OEt 5-CF₃ Bn 72-73 B1-23a 4-Me—Ph 5-CF₃ Me 142-145 B1-24a 4-F—Ph 5-CF₃ Me 133-135 B1-25a 4-CF₃—Ph 5-CF₃ Me 170-171 B1-26a 3-MeO—Ph 5-CF₃ Me 135-142 B1-27a 2-MeO—Ph 5-CF₃ Me *1 B1-28a i-Pr 5-CF₂H Me 142-145 B1-29a D-8a 5-CF₃ Me *1 B1-30a D-9a 5-CF₃ Me 140-145 B1-31a D-10a 5-CF₃ Me 126-129 B1-32a D-11 5-CF₃ Me 122-124 B1-33a D-12 5-CF₃ Me 171-172 B1-34a D-13a 5-CF₃ Me *1 B1-35b CH₂OC(O)Me 5-CF₃ Bn 88-89 B1-36a CH₂(4-MeO—Ph) 5-CF₃ Me  92-110 B1-37c i-Pr 5-CF₂CF₃ Et 57-58 B1-38a 3,5-(MeO)₂—Ph 5-CF₃ Me 150-161 B1-39a 3,5-(Cl)₂—Ph 5-CF₃ Me 157-164 B1-40a i-Pr 5-CF₃-6-Me Me 58-59 B1-41c i-Pr 5-CF₃-7-Me Et 76-77 B1-42a (CH₂)₂SMe 5-CF₃ Me 126-127 B1-43a CH(Me)SMe 5-CF₃ Me 103-104 B1-44c i-Pr 5-Ph Et 133-134 B1-45c i-Pr 5-{3,5-(F)₂—Ph} Et 125-127 B1-46a NMe₂ 5-CF₃ Me 135-137 B1-47c D-14 5-CF₃ Et 138-139 B1-48a CH₂(c-Pr) 5-CF₃ Me 130-135 B1-49a D-16a 5-CF₃ Me *1 B1-50a C≡CMe 5-CF₃ Me 163-168

TABLE 44 Melting No. R¹ ^(a) (R^(2a))n Z¹ point (° C.) B1-51a CH₂CF₃ 5-CF₃ Me 150-154 B1-52a CH₂CN 5-CF₃ Me 165-170 B1-53c D-16m 5-CF₃ Et  95-102 B1-54c D-24f 5-CF₃ Et 101-110 B1-55c (CH₂)₂OMe 5-CF₃ Et 82-83

Reference Example 3

Compounds listed in Fourteenth Table were synthesized by a similar method to Step 3 of Synthesis Example 7. In Tables, Me is methyl group. Similarly, Et is ethyl group, Pr is propyl group, Pen is pentyl group, Ph is phenyl group, Bn is benzyl group, n- is normal, i- is iso, c- is cyclo, and t- is tertiary.

In Tables, substituents of D-3a, D-4a, D-5, D-8a, D-9a, D-10a, D-11, D-12, D-13a, D-14, D-16a, D-16m and D-24f are the following structures.

In Tables, “1” is “Resinous”. ¹H-NMR data of compounds that have no melting points are listed in Sixteenth Table.

FOURTEENTH TABLE

TABLE 45 Melting No. R¹ ^(a) (R^(2a))n point (° C.) C1-01 H 5-CF₃ *1 C1-02 c-Pr 5-CF₃ *1 C1-03 3-Pen 5-CF₃ 137-139 C1-04 Ph 5-CF₃ *1 C1-05 CH₂OMe 5-CF₃ 111-112 C1-06 4-MeO—Ph 5-CF₃ 215-218 C1-07 4-Cl—Ph 5-CF₃ 241-247 C1-08 CH₂O(CH₂)₂OMe 5-CF₃ 47-49 C1-09 CH₂OCH₂CF₃ 5-CF₃ 67-70 C1-10 CH(CH₃)CH₂CH₃ 5-CF₃ 137-140 C1-11 D-3a 5-CF₃ 197-201 C1-12 i-Pr 6-CF₃ 224-226 C1-13 n-Pr 5-CF₃ 134-135 C1-14 CH₂OPh 5-CF₃ 136-140 C1-15 c-Pen 5-CF₃ 156-158 C1-16 D-5 5-CF₃ 195-200 C1-17 CH₂OEt 5-CF₃ 96-97 C1-18 t-Bu 5-CF₃ 125-131 C1-19 D-4a 5-CF₃ 184-186 C1-20 CH₂SMe 5-CF₃ 110-111 C1-21 CH₂SCH₂CF₃ 5-CF₃ 56-59 C1-22 CH₂C(O)OEt 5-CF₃ 124-126 C1-23 4-Me—Ph 5-CF₃ 250-253 C1-24 4-F—Ph 5-CF₃ 249-251 C1-25 4-CF₃—Ph 5-CF₃ 199-201 C1-26 3-MeO—Ph 5-CF₃ 179-181 C1-27 2-MeO—Ph 5-CF₃ 85-90 C1-28 i-Pr 5-CF₂H 193-195 C1-29 D-8a 5-CF₃ 237-240 C1-30 D-9a 5-CF₃ 231-234 C1-31 D-10a 5-CF₃ 215-220 C1-32 D-11 5-CF₃ 190-195 C1-33 D-12 5-CF₃ 218-223 C1-34 D-13a 5-CF₃ 185-188 C1-35 CH₂OC(O)Me 5-CF₃ 126-128 C1-36 CH₂(4-MeO—Ph) 5-CF₃ 73-75 C1-37 i-Pr 5-CF₂CF₃ 170-175 C1-38 3,5-(MeO)₂—Ph 5-CF₃ 158-160 C1-39 3,5-(Cl)₂—Ph 5-CF₃ 250-252 C1-40 i-Pr 5-CF₃-6-Me 153-154 C1-41 i-Pr 5-CF₃-7-Me 190-192 C1-42 (CH₂)₂SMe 5-CF₃ 149-151 C1-43 CH(Me)SMe 5-CF₃ 145-146 C1-44 i-Pr 5-Ph 218-219 C1-45 i-Pr 5-{3,5-(F)₂—Ph} 210-220 C1-46 NMe₂ 5-CF₃ 181-183 C1-47 D-14 5-CF₃ 210-213 C1-48 CH₂(c-Pr) 5-CF₃ 109-114

TABLE 46 Melting No. R¹ ^(a) (R^(2a))n point (° C.) C1-49 D-16a 5-CF₃ 159-164 C1-50 C≡CMe 5-CF₃ 234-238 C1-51 CH₂CF₃ 5-CF₃ 168-171 C1-52 CH₂CN 5-CF₃ 227-231 C1-53 D-16m 5-CF₃ 118-120 C1-54 D-24f 5-CF₃ 169-170 C1-55 (CH₂)₂OMe 5-CF₃ 104-105

Reference Example 4 3-(Ethylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid Step 1; Synthesis of 3-(thioxo)-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

To 20 ml of methanol solution of 2.0 g of methyl 3-thioxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate synthesized by a similar method to Step 1 of Synthesis Example 8 containing imidazole, 17 ml of 0.5 mol/L sodium hydroxide aqueous solution was added under cooling with ice. After completion of the addition, the reaction solution was stirred at room temperature for 3.5 hours. After completion of the reaction, 20 ml of 1 mol/L hydrochloric acid was added to the reaction solution and the precipitated solid in the reaction solution was separated by filtration. The obtained solid was washed with 1 mol/L hydrochloric acid, water, and diisopropyl ether in this order and filtered to give 1.1 g of the target product as a yellow solid.

Melting point: 235° C. to 240° C.

Step 2; Synthesis of 3-(ethylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

To 10 ml of N,N-dimethylformamide solution of 700 mg (2.66 mmol) of 3-(thioxo)-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid, 898 mg (5.76 mmol) of ethyl iodide was added at room temperature. After completion of the addition, the reaction solution was stirred at room temperature for 4 days. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure. To the obtained residue, 5 ml of water and 5 ml of 1 mol/l hydrochloric acid were added and the precipitated solid was separated by filtration. The obtained solid was washed with water and diisopropyl ether in this order to give 486 mg of the target product as a yellow solid.

Melting point: 113° C. to 114° C.

Reference Example 5

The following compounds were synthesized by similar methods to Step 2 and Step 3 of Synthesis Example 8 or Reference Example 4.

Methyl 3-(isopropylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 120° C. to 122° C.

3-(Isopropylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 135° C. to 136° C.

3-((2-Methoxyethyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carbo xylic acid

Melting point: 106° C. to 111° C.

3-(Allylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 96° C. to 99° C.

3-(Prop-2-yn-1-ylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 179° C. to 181° C.

Methyl 3-(n-propylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 87° C. to 88° C.

3-(n-Propylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 106° C. to 108° C.

Methyl 3-(isobutylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 105° C. to 106° C.

3-(Isobutylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 110° C. to 112° C.

Methyl 3-(s-butylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 88° C. to 90° C.

3-(s-Butylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 107° C. to 109° C.

Methyl 3-(benzylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 130° C. to 135° C.

3-(Benzylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 153° C. to 156° C.

Methyl 3-((4-methoxybenzyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 119° C. to 121° C.

3-((4-Methoxybenzyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 180° C. to 182° C.

Methyl 3-((cyclopropylmethyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 122° C. to 123° C.

3-((Cyclopropylmethyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 127° C. to 129° C.

Methyl 3-(((tetrahydrofuran-2-yl)methyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

¹H NMR (CDCl₃, Me₄Si, 300 MHz) δ 7.95 (d, 1H, J=7.2 Hz), 7.42 (d, 1H, J=7.2 Hz), 4.34-4.25 (m, 1H), 4.09 (s, 3H), 3.92-3.84 (m, 1H), 3.79-3.68 (m, 2H), 3.56-3.49 (m, 1H), 2.17-2.06 (m, 1H), 1.99-1.87 (m, 2H), 1.76-1.68 (m, 1H).

3-(((Tetrahydrofuran-2-yl)methyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyri dine-8-carboxylic acid

Melting point: 108° C. to 112° C.

Methyl 3-((cyanomethyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 146° C. to 148° C.

3-((Cyanomethyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 138° C. to 140° C.

Methyl 3-((2-oxopropyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 84° C. to 87° C.

3-((2-Oxopropyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 121° C. to 124° C.

Methyl 3-(((1,3-dioxolan-2-yl)methyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 99° C. to 102° C.

3-(((1,3-Dioxolan-2-yl)methyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 110° C. to 112° C.

3-((2,2,2-Trifluoroethyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 150° C. to 151° C.

3-((2-methoxy-2-oxoethyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 143° C. to 144° C.

Methyl 3-(cyclopentylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 92° C. to 94° C.

3-(Cyclopentylthio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 143° C. to 146° C.

Methyl 3-(((6-chloropyridin-3-yl)methyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 99° C. to 100° C.

3-(((6-Chloropyridin-3-yl)methyl)thio)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 159° C. to 160° C.

Reference Example 6 Synthesis of methyl 2-methyl-3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

To the mixture of 500 mg (1.91 mmol) of methyl 3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate, 525 mg (3.82 mmol) of potassium carbonate, and 10 ml of acetonitrile, 298 mg (2.10 mmol) of methyl iodide was added at room temperature. After completion of the addition, the reaction solution was stirred at room temperature for 5 hours. After completion of the reaction, 20 ml of chloroform was added to the reaction solution and the precipitated solid was separated by filtration. The solvent in the solution obtained by the filtration was distilled away under reduced pressure. The obtained residue after distilling the solvent away was purified with the medium pressure preparative liquid chromatography eluting the residue with n-hexane-ethyl acetate (gradient from 17:3 to 2:3) to give 312 mg of the target product as a yellow solid.

Melting point: 189° C. to 190° C.

The following compounds were synthesized by a similar method.

Methyl 2-ethyl-3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 135° C. to 137° C.

Methyl 2-isopropyl-3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 124° C. to 125° C.

Methyl 2-benzyl-3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

Melting point: 99° C. to 100° C.

Reference Example 7 Synthesis of 2-methyl-3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

To 3 ml of ethanol solution of 312 mg (1.13 mmol) of methyl 2-methyl-3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate, 3 ml of aqueous solution of 50 mg (1.25 mmol) of sodium hydroxide was added under cooling with ice. After completion of the addition, the reaction solution was stirred for 1 hour at the same temperature. After completion of the reaction, 3 ml of 1 mol/L hydrochloric acid was added to the reaction solution and the resultant mixture was extracted with dichloromethane (10 ml, 3 times). The obtained organic phase was dehydrated and dried with saturated sodium chloride aqueous solution and anhydrous sodium sulfate in this order and the solvent was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether and filtered to give 250 mg of the target product as a yellow solid.

Melting point: 155° C. to 160° C.

The following compounds were synthesized by a similar method.

2-Ethyl-3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carb oxylic acid

Melting point: 160° C. to 163° C.

2-Isopropyl-3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 160° C. to 162° C.

2-Benzyl-3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

Melting point: 84° C. to 86° C.

Reference Example 8 Synthesis of methyl 3-thioxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

100 mg of the mixture of methyl 3-thioxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate synthesized by the method of Step 1 of Synthesis Example 8 and imidazole was dissolved in 50 ml of ethyl acetate and the resultant mixture was washed with 20 ml of 1 mol/L hydrochloric acid. The obtained organic phase was dried over anhydrous sodium sulfate and the solvent was distilled away under reduced pressure to give 63 mg of the target product as an orange-yellow solid.

Melting point: 218° C. to 220° C.

Reference Example 9 3-(Phenylamino)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid Step 1; Synthesis of methyl 2-(2-(phenylcarbamoyl)hydrazinyl)-6-(trifluoromethyl)nicotinate

To 13 ml of tetrahydrofuran solution of 500 mg (2.13 mmol) of methyl 2-hydrazinyl-6-(trifluoromethyl)nicotinate, 255 mg (2.14 mmol) of phenyl isocyanate was added under cooling with ice. After completion of the addition, the reaction solution was stirred for 14 hours at the same temperature. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure. The precipitated solid was washed with diisopropyl ether to give 740 mg of the target product as a white solid.

Melting point: 190° C. to 195° C.

Step 2; Synthesis of methyl 3-(phenylamino)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

To the mixed solution of 730 mg (2.06 mmol) of methyl 2-(2-(phenylcarbamoyl)hydrazinyl)-6-(trifluoromethyl)nicotinate and 15 ml of toluene, 940 mg (6.11 mmol) of phosphoryl chloride was added at room temperature. After completion of the addition, the reaction mixture was stirred for 3 hours under heating to reflux. After completion of stirring, the reaction mixture was cooled to room temperature and added to ice-water to terminate the reaction. Thereafter, the reaction liquid was extracted with ethyl acetate (30 ml, 2 times). The obtained organic phase was dried over anhydrous sodium sulfate and the solvent was distilled away under reduced pressure. The obtained residue was purified with the medium pressure preparative liquid chromatography eluting the residue with n-hexane-ethyl acetate-methanol (gradient from 90:10:0 to 0:100:0 to 0:90:10) to give 480 mg of the target product as a yellow solid.

Melting point: 225° C. to 230° C.

Step 3; Synthesis of 3-(phenylamino)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

To the mixed solution of 470 mg (1.40 mmol) of methyl 3-(phenylamino)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate and 10 ml of methanol, 8.0 ml (8.0 mmol) of 1 mol/L sodium hydroxide aqueous solution was added under cooling with ice. After completion of the addition, the reaction solution was stirred for 3 hours under cooling with ice. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure and thereafter 1 N hydrochloric acid was added to the reaction solution to adjust the pH to 5 to 6. The reaction mixed liquid was extracted with ethyl acetate (30 ml, 2 times) and the obtained organic phase was dried over anhydrous sodium sulfate, followed by distilling the solvent away under reduced pressure. The precipitated solid was washed with diisopropyl ether to give 250 mg of the target product as an orange solid.

Melting point: 125° C. to 130° C.

Reference Example 10 3-((2-Methoxyethyl)(methyl)amino)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid Step 1; Synthesis of ethyl 2-(2-((2-methoxyethyl)(methyl)carbamoyl)hydrazinyl)-6-(trifluoromethyl)nicotinate

A mixture of 500 mg (1.82 mmol) of ethyl 3-oxo-5-(trifluoromethyl)-2,3-dihydro-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate, 320 mg (3.59 mmol) of N-(2-methoxyethyl)methylamine, and 10 ml of tetrahydrofuran was stirred for 3 hours under heating to reflux. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure. The obtained residue was purified with the medium pressure preparative liquid chromatography eluting the residue with n-hexane-ethyl acetate (gradient from 90:10 to 0:100) to give 610 mg of the target product as a light yellow solid.

Melting point: 65° C. to 66° C.

Step 2; Synthesis of ethyl 3-((2-methoxyethyl)(methyl)amino)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate

To the mixed solution of 595 mg (1.63 mmol) of ethyl 2-(2-((2-methoxyethyl)(methyl)carbamoyl)hydrazinyl)-6-(trifluoromethyl)nicotinate and 10 ml of toluene, 750 mg (4.94 mmol) of phosphoryl chloride was added at room temperature. After completion of the addition, the reaction mixture was stirred for 1.5 hours under heating to reflux. After completion of stirring, the reaction mixture was cooled to room temperature and added to ice-water to terminate the reaction. Subsequently sodium hydrogen carbonate aqueous solution was added to adjust the pH to 8 to 9. Thereafter, the resultant mixture was extracted with ethyl acetate (30 ml, 2 times). The obtained organic phase was dried over anhydrous sodium sulfate and the solvent was distilled away under reduced pressure. The obtained residue was purified with the medium pressure preparative liquid chromatography eluting the residue with n-hexane-ethyl acetate (gradient from 90:10 to 0:100) to give 520 mg of the target product as an orange liquid.

¹H NMR (CDCl₃, Me₄Si, 300 MHz) δ 7.91 (d, 1H, J=7.2 Hz), 7.80 (d, 1H, J=7.2 Hz), 4.55 (q, 2H, J=6.9 Hz), 3.75-3.41 (m, 4H), 3.27 (s, 3H), 2.87 (s, 3H), 1.48 (t, 3H, J=6.9 Hz).

Step 3; Synthesis of 3-((2-methoxyethyl)(methyl)amino)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylic acid

To the mixed solution of 500 mg (1.44 mmol) of ethyl 3-((2-methoxyethyl)(methyl)amino)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxylate and 10 ml of ethanol, 4.5 ml (4.5 mmol) of 1 mol/L sodium hydroxide aqueous solution was added under cooling with ice. After completion of the addition, the reaction solution was stirred for 1 hour under cooling with ice. After completion of the reaction, the solvent in the reaction solution was distilled away under reduced pressure and thereafter 1 mol/L hydrochloric acid was added to the reaction solution to adjust the pH to 4. The reaction mixed liquid was extracted with ethyl acetate (30 ml, 2 times) and the obtained organic phase was dried over anhydrous sodium sulfate, followed by distilling the solvent away under reduced pressure to give 470 mg of the target product as a light yellow solid.

Melting point: 115° C. to 120° C.

Reference Example 11

Compounds listed in Fifteenth Table were synthesized by a similar method to Reference Example 9 or Reference Example 10. In Tables, Me is methyl group. Similarly, Et is ethyl group, Ph is phenyl group, and c- is cyclo.

In Tables, substituents of D-9b, D-14, D-17, and D-19 are the following structures.

FIFTEENTH TABLE

TABLE 47 Melting No. R^(1 a) (R^(2a))n Z¹ point (° C.) C2-01 N(Me)Ph 5-CF₃ H 160-170 C2-02 NHCH(CH₃)₂ 5-CF₃ H 145-146 C2-03 D-14 5-CF₃ H 210-213 C2-04 NH(D-9b) 5-CF₃ H 170-174 C2-05 NH(CH₂)₂OMe 5-CF₃ H 150-155 C2-06 NHSO₂Ph 5-CF₃ H >290 C2-07 D-17 5-CF₃ H 160-165 C2-08 NH(CH₂)₂SMe 5-CF₃ H 173-176 C2-09 NHCH₂CF₃ 5-CF₃ H 180-183 C2-10 N(Me)CH(CH₃)₂ 5-CF₃ H 135-137 C2-11 N(Me)Hex-c 5-CF₃ H 184-186 C2-12 N(Me)Et 5-CF₃ H 140-141 C2-13 N(Et)₂ 5-CF₃ H 126-127 C2-14 D-19 5-CF₃ H 150-151 C2-15 N(Me)CH₂C≡CH 5-CF₃ H 133-134 C2-16 N(Me)(CH₂)₂CN 5-CF₃ H 136-137 C2-17 N(Me)(4-MeO—Ph) 5-CF₃ H 168-171 C2-18 N(Me)CH₂CH═CH₂ 5-CF₃ H 117-118 C2-19 N(Me)CH₂(4-MeO—Ph) 5-CF₃ H 105-110

[Sixteenth Table]

TABLE 48 No. ¹H-NMR (CDCl₃, Me₄Si, 300 MHz) A1-01a δ10.02 (brs, 1H), 8.34 (d, 1H, J = 7.8 Hz), 8.26 (s, 1H), 8.23 (brs, 1H), 7.11 (d, 1H, J = 7.8 Hz), 3.96 (s, 3H)∘ A1-04a δ10.21 (d, 1H, J = 6.0 Hz), 8.84 (d, 1H, J = 5.7 Hz), 8.35 (dd, 1H, J = 7.2 Hz, 0.9 Hz), 7.88-7.85 (m, 2H), 7.56-7.46 (m, 3H), 7.08 (d, 1H, J = 7.8 Hz), 3.98 (s, 3H)∘ A1-08a δ9.70 (brs, 1H), 9.26 (brs, 1H), 8.32 (d, 1H, J = 7.8 Hz), 7.07 (d, 1H, J = 7.8 Hz), 4.21 (s, 2H), 3.95 (s, 3H), 3.89-3.86 (m, 2H), 3.65-3.62 (m, 2H), 3.40 (s, 3H)∘ B1-01a δ9.04 (d, 1H, J = 1.8 Hz), 8.14 (d, 1H, J = 6.6 Hz), 7.41 (d, 1H, J = 6.6 Hz), 4.13 (s, 3H)∘ B1-02a δ7.95 (d, 1H, J = 7.5 Hz), 7.44 (d, 1H, J = 7.5 Hz), 4.09 (s, 3H), 2.32-2.25 (m, 1H), 1.38-1.33 (m, 2H), 1.22-1.16 (m, 2H)∘ B1-04a δ8.04 (dd, 1H, J = 7.2 Hz, 0.6 Hz), 7.60-7.42 (m, 6H), 4.14 (s, 3H)∘ B1-08a δ8.04 (d, 1H, J = 7.2 Hz), 7.49 (d, 1H, J = 7.2 Hz), 5.21 (d, 2H, J = 0.9 Hz), 4.11 (s, 3H), 3.75-3.72 (m, 2H), 3.54-3.51 (m, 2H), 3.33 (s, 3H)∘ B1-27a δ8.04 (d, 1H, J = 7.5 Hz), 7.45-7.60 (m, 1H), 7.35-7.45 (m, 2H), 7.00-7.15 (m, 1H), 6.90-7.00 (m, 1H), 4.13 (s, 3H), 3.65 (s, 3H)∘ B1-29a δ8.49 (s, 1H), 8.00-8.15 (m, 1H), 7.75-7.85 (m, 1H), 7.40-7.60 (m, 2H), 4.13 (s, 3H)∘ B1-34a δ8.17 (d, 1H, J = 7.2 Hz), 7.70 (d, 1H, J = 8.1 Hz), 7.54 (d, 1H, J = 7.2 Hz), 7.35-7.45 (m, 2H), 7.20-7.30 (m, 2H), 4.17 (s, 3H), 3.54 (s, 3H)∘ B1-49a δ8.00 (d, 1H, J = 7.5 Hz), 7.54 (d, 1H, J = 7.5 Hz), 4.10 (s, 3H), 2.91 (d, 1H, J = 7.5 Hz), 1.91 (d, 1H, J = 7.5 Hz), 1.85 (s, 3H)∘ C1-01 δ9.06 (d, 1H, J = 1.5 Hz), 8.33 (d, 1H, J = 7.2 Hz), 7.57 (d, 1H, J = 6.9 Hz)∘ (Proton peak of CO₂H was not observed.) C1-02 δ8.38 (d, 1H, J = 7.5 Hz), 7.60 (d, 1H, H = 7.5 Hz), 2.39-2.28 (m, 1H), 1.42-1.35 (m, 2H), 1.29-1.23 (m, 2H)∘ (Proton peak of CO₂H was not observed.) C1-04 δ8.30 (d, 1H, J = 6.9 Hz), 7.60-7.49 (m, 6H)∘ (Proton peak of CO₂H was not observed.)

TEST EXAMPLES

Subsequently, usefulness of the compound of the present invention as a herbicide will be specifically described in the following Test Examples. The present invention, however, is not limited to these Test Examples.

Test Example 1 Herbicidal Activity Test by Application Before Weed Generation in Submerged Conditions

After alluvial soil was placed into 1/10000 are of Wagner pot, water was poured and mixed to form a submerged condition having a water depth of 4 cm. Seeds of Echinochloa oryzacola Vasing., Scirpus juncoides, and Monochoria vaginalis were sowed in a mixed manner in the above pot and thereafter 2.5 leaf stage Oryza sativa seedling was transplanted. On the day of sowing seeds, the emulsion agent containing the compound of the present invention prepared in accordance with Formulation Example 2 was diluted with water so as to be a predetermined herbicide amount and the diluted compound was applied to the surface of the water. The pot was placed in a greenhouse of 25° C. to 30° C. to grow plant. Three weeks after the herbicide application, effects on each plant were investigated in accordance with the following criteria. The results are listed in Seventeenth Table.

Criteria

5 Herbicidal ratio of 90% or more (almost completely withered) 4 Herbicidal ratio of 70% or more and less than 90% 3 Herbicidal ratio of 40% or more and less than 70% 2 Herbicidal ratio of 20% or more and less than 40% 1 Herbicidal ratio of 5% or more and less than 20% 0 Herbicidal ratio of 5% or less (almost no effect)

Test Example 2 Herbicidal Activity Test by Application During Weed Generation in Submerged Conditions

After alluvial soil was placed into 1/10000 are of Wagner pot, water was poured and mixed to form a submerged condition having a water depth of 4 cm. Seeds of Echinochloa oryzacola Vasing., Scirpus juncoides, and Monochoria vaginalis were sowed in a mixed manner in the above pot and the pot was placed in the greenhouse of 25° C. to 30° C. to grow the plants. When Echinochloa oryzacola Vasing., Scirpus juncoides, and Monochoria vaginalis were grown to one leaf stage to two leaf stage, the emulsion agent containing the compound of the present invention prepared in accordance with Formulation Example 2 was diluted with water so as to be a predetermined herbicide amount and the diluted compound was applied to the surface of the water. Three weeks after the herbicide application, effects on each plant were investigated in accordance with the criteria of Test Example 1. The results are listed in Eighteenth Table.

Test Example 3 Herbicidal Effect Test by Application to Foliage

After alluvial soil was placed into 1/10000 are of Wagner pot, water was poured and mixed to form a condition having a water depth of 0.1 cm to 0.5 cm. Seeds of Echinochloa crus-galli var. crus-galli, Leptochloa chinensis, Cyperus difformis, and Oryza sativa were sowed and the pot was placed in the greenhouse of 25° C. to 30° C. to grow the plants. After the plants were grown for 14 days, the emulsion agent containing the compound of the present invention prepared in accordance with Formulation Example 2 was diluted with water so as to be a predetermined herbicide amount and the diluted compound was uniformly applied to a stem and leaf part with a small-size spray. Three weeks after the herbicide application, effects on each plant were investigated in accordance with the criteria of Test Example 1. The results are listed in Nineteenth Table.

Test Example 4 Herbicidal Effect Test by Application to Foliage

Sterilized diluvial soil was placed in a plastic box having a length of 21 cm, a width of 13 cm, and a depth of 7 cm. Each of the seeds of Digitaria ciliaris, Setaria viridis, Echinochloa crus-galli var. crus-galli, Avena fatua, Alopecurus myosuroides, Lolium multiflorum Lam., Apera spica-venti., Abutilon theophrasti, Amaranthus retroflexus, Chenopodium album, Stellaria media, Galium spurium, Veronica persica, Zea mays, Glycine max, Oryza sativa, Triticum aestivum, Beta vulgaris ssp. vulgaris, and Brassica campestris L. was sowed in a spot-like manner and was covered with the soil of about 1.5 cm thick. Thereafter, the plants were grown in the greenhouse of 25° C. to 30° C. After the plants were grown for 14 days, the emulsion agent containing the compound of the present invention prepared in accordance with Formulation Example 2 was diluted with water so as to be a predetermined herbicide amount and the diluted compound was uniformly applied to a stem and leaf part with a small-size spray. Three weeks after the herbicide application, effects on each plant were investigated in accordance with the criteria of Test Example 1. The results are listed in Twentieth Table.

The symbols in Seventeenth Table to Twentieth Table have the following meanings.

A: Echinochloa oryzicola Vasing., B: Scirpus juncoides, C: Monochoria vaginalis, D: Leptochloa chinensis, E: Cyperus difformis, F: Digitaria ciliaris, G: Setaria viridis, H: Echinochloa crus-galli var. crus-galli, I: Avena fatua, J: Alopecurus myosuroides, K: Lolium multiflorum Lam., L: Apera spica-venti., M: Abutilon theophrasti, N: Amaranthus retroflexus, O: Chenopodium album, P: Stellaria media, Q: Galium spurium, R: Veronica persica, a: transplanted Oryza sativa, b: directly sowed Oryza sativa, c: Zea mays, d: Glycine max, e: Triticum aestivum, f: Beta vulgaris ssp. vulgaris, and g: Brassica campestris L.

The application herbicide amount (g/ha) means an amount that a concentration is adjusted so that, when an application amount is converted into per hectare (1 ha), the herbicide is applied by the number of grams (g) of the described value.

[Seventeenth Table]

TABLE 49 Application herbicide No. amount (g/ha) A B C a 1-001 320 3 2 2 0 1-002 320 2 1 0 0 1-004 320 5 4 4 1 1-005 320 5 4 4 0 1-010 320 5 3 0 1-011 320 5 4 5 1 1-012 320 5 3 4 0 1-014 320 5 4 3 0 1-015 320 2 3 3 0 1-016 320 4 0 0 0 1-017 320 3 2 0 0 1-018 320 1 3 5 0 1-019 320 5 3 4 2 1-020 320 4 3 2 0 1-021 320 5 4 4 2 1-022 320 2 2 0 0 1-024 320 5 2 0 0 1-026 320 5 4 4 2 1-027 320 5 3 4 1 1-029 320 5 3 4 2 1-030 320 5 3 3 0 1-031 320 4 3 3 0 1-032 320 5 3 2 2 1-033 320 5 4 3 0 1-034 320 4 4 4 3 1-035 320 5 4 4 2 1-036 320 4 3 3 4 1-037 320 0 2 3 0 1-038 320 2 2 1 0 1-040 320 3 3 3 1 1-041 320 3 3 3 0 1-042 320 2 2 2 0 1-043 320 5 3 3 3 1-044 320 5 3 3 1 1-046 320 5 3 3 2 1-047 320 4 3 2 1 1-048 320 3 0 0 1 1-049 320 5 2 0 0 1-050 320 5 5 4 2 1-051 320 5 4 4 0 1-052 320 3 3 2 0 1-053 320 2 3 2 0 1-054 320 5 3 4 2 1-055 320 4 4 4 1 1-056 320 5 5 4 3 1-057 320 5 5 4 2 1-058 320 5 5 4 4

TABLE 50 Application herbicide No. amount (g/ha) A B C a 1-059 320 2 3 2 0 1-060 320 4 4 3 2 1-062 320 3 2 1 0 1-063 320 5 4 3 0 1-064 320 5 4 3 0 1-065 320 5 3 2 0 1-066 320 5 4 2 2 1-067 320 3 0 0 0 1-068 320 2 3 3 0 1-069 320 5 4 3 0 1-070 320 5 5 5 3 1-071 320 4 5 4 0 1-073 320 4 3 2 3 1-074 320 2 2 0 0 1-075 320 2 0 2 0 1-076 320 5 4 4 3 1-077 320 0 0 2 0 1-078 320 4 4 3 4 1-079 320 4 4 3 4 1-080 320 5 4 4 4 1-082 320 3 2 2 0 1-083 320 2 3 3 0 1-084 320 2 3 2 0 1-085 320 3 4 3 3 1-086 320 5 4 4 5 1-087 320 5 3 0 1-090 320 3 4 2 0 1-091 320 5 5 5 0 1-092 320 5 5 4 3 1-093 320 5 4 3 0 1-094 320 5 5 3 0 1-095 320 5 5 5 1 1-096 320 5 4 4 3 1-100 320 4 3 3 0 1-102 320 3 2 2 2 1-103 320 5 4 4 3 1-104 320 4 3 2 0 1-105 320 5 5 4 0 1-106 320 5 5 4 1 1-107 320 5 4 5 2 1-108 320 5 5 5 0 1-109 320 0 2 0 0 1-110 320 5 4 4 4 1-112 320 3 3 2 0 1-113 320 4 3 2 0 1-114 320 3 2 0 0 1-115 320 5 4 3 0

TABLE 51 Application herbicide No. amount (g/ha) A B C a 1-116 320 5 4 2 0 1-118 320 3 2 0 2 1-119 320 2 1 0 3 1-120 320 5 3 1 3 1-121 320 5 4 4 3 1-122 320 5 5 5 3 1-123 320 5 4 4 1 1-124 320 3 3 1 0 1-125 320 0 3 1 0 1-126 320 3 4 2 0 1-128 288 5 4 2 0 1-129 320 5 4 3 1 1-130 320 1 0 0 1 1-131 320 2 1 0 0 1-132 320 5 4 4 2 1-133 320 5 3 4 0 1-134 320 3 3 2 0 1-135 320 3 4 4 1 1-136 320 5 3 3 1 1-137 320 5 5 5 3 1-138 320 5 5 4 2 1-139 320 5 4 3 2 1-143 320 0 0 2 0 1-144 320 5 3 3 1 1-145 320 5 5 5 4 1-146 320 5 5 5 3 1-147 320 5 5 5 2 1-148 320 5 5 5 4 1-149 320 5 4 3 3 1-150 320 5 5 5 4 1-151 320 5 5 3 0 1-152 320 5 4 3 2 1-153 320 3 3 4 2 1-154 320 3 2 0 1-155 320 4 3 0 1-156 320 2 0 0 1-157 320 3 2 2 1-158 320 4 0 0 1-159 320 3 0 0 1-161 320 2 0 0 1-162 320 2 0 0 1-163 320 4 4 2 1-164 320 5 4 3 1-165 320 4 3 4 0 1-166 320 3 2 0 1-167 320 4 2 0 0 1-169 320 5 4 4 0

TABLE 52 Application herbicide No. amount (g/ha) A B C a 1-171 320 5 4 4 1 1-172 320 5 4 3 1 2-001 320 2 3 4 0 2-002 320 2 3 3 0 2-003 320 5 5 5 4 2-005 320 5 5 5 0 2-006 320 5 5 5 4 2-007 320 5 5 5 3 2-008 320 4 4 4 1 2-009 320 3 3 4 0 2-010 320 5 5 4 4 2-011 320 5 5 5 2 2-012 320 5 4 3 1 2-013 320 5 4 5 3 2-014 320 5 5 5 4 2-015 320 5 5 5 1 2-016 320 5 5 5 4 2-017 320 5 3 4 4 2-019 320 5 5 4 2 2-020 320 3 2 2 1 2-021 320 5 5 5 4 2-022 320 5 5 5 5 2-023 320 2 1 0 3 2-024 320 5 5 5 5 2-025 320 5 5 5 5 2-026 320 5 5 4 4 2-027 320 5 5 5 4 2-028 320 5 5 5 5 2-029 320 5 5 5 5 2-030 320 5 4 4 3 2-031 320 5 5 5 5 2-032 320 5 5 5 5 2-033 320 5 4 5 4 2-034 320 5 4 4 4 2-035 320 4 3 3 4 2-037 320 5 5 5 4 2-038 320 5 5 5 4 2-039 320 5 5 5 4 2-040 320 4 4 4 4 2-041 320 5 5 4 0 2-042 320 5 4 4 5 2-043 320 5 5 5 4 2-044 320 5 5 5 4 2-045 320 5 5 5 5 2-046 320 4 0 0 0 2-047 320 5 4 5 4 2-048 320 5 5 4 4

TABLE 53 Application herbicide No. amount (g/ha) A B C a 2-049 320 5 5 4 3 2-050 192 4 2 3 2 2-051 320 5 5 5 4 2-052 320 5 5 5 5 2-053 320 5 5 4 5 2-054 320 5 5 5 5 2-056 320 4 4 3 1 2-057 320 4 4 4 4 2-058 320 4 4 5 5 2-059 320 4 4 4 5 2-060 320 5 5 5 5 2-061 320 5 5 5 4 2-062 320 5 5 5 5 2-063 320 5 5 4 2-064 320 5 2 3 2-065 320 5 4 4 2 2-066 320 5 5 4 3 2-067 320 5 4 4 5 2-068 320 5 5 4 5 2-069 320 5 5 5 5 2-070 320 5 5 5 4 2-071 320 5 5 5 4 2-072 320 5 5 5 3 2-073 320 4 3 4 2 2-074 320 4 4 3 3 2-075 320 5 5 5 5 2-076 320 5 4 3 2 2-077 320 5 3 3 1 2-078 320 5 4 2 4 2-079 320 5 5 5 4 2-080 320 3 0 0 2 2-081 320 4 3 4 3 2-082 320 5 5 5 5 2-083 320 5 5 4 2 2-084 320 5 5 4 4 2-085 320 5 5 4 1 2-086 320 3 2 3 0 2-087 320 5 5 4 3 2-088 141 5 5 5 3 2-089 320 5 5 5 4 2-090 320 5 5 5 4 2-091 320 5 5 5 0 2-093 320 5 5 4 2 2-094 320 5 5 5 4 2-095 320 5 5 5 5 2-096 320 5 4 3 2-097 320 4 3 1

TABLE 54 Application herbicide No. amount (g/ha) A B C a 2-098 320 5 4 2 2-099 320 5 4 5 4 2-100 320 5 5 5 3 2-101 320 5 5 5 3 2-102 320 5 5 4 1 2-103 320 5 4 5 3 2-105 320 5 5 5 4 2-106 320 5 3 4 2 2-107 320 2 3 2 1 2-108 320 4 3 2 0 2-109 260 2 3 0 2-110 320 5 5 5 4 4-003 320 2 0 0 6-002 320 4 3 2 0 6-004 320 0 0 2 0 7-001 320 0 2 4 0 7-002 320 3 3 4 1

[Eighteenth Table]

TABLE 55 Application herbicide No. amount (g/ha) A B C 1-001 320 4 4 2 1-002 320 3 0 0 1-004 320 4 3 4 1-005 320 5 1 0 1-010 320 4 1 4 1-011 320 5 3 3 1-012 320 2 2 2 1-014 280 2 3 0 1-015 320 4 2 1 1-016 320 3 0 0 1-017 320 2 2 0 1-018 320 0 2 0 1-019 320 4 3 3 1-020 320 2 2 2 1-021 320 4 4 3 1-022 320 2 2 0 1-024 320 4 1 0 1-026 320 3 1 0 1-027 320 4 3 3 1-029 320 3 2 3 1-030 320 4 3 3 1-031 320 3 2 2 1-032 320 4 3 3 1-033 320 4 4 3 1-034 320 4 3 4 1-035 320 5 4 4 1-036 320 3 2 4 1-037 320 2 2 1-038 320 1 1 0 1-040 320 3 2 1-041 320 2 3 1-042 320 1 2 3 1-043 320 3 3 3 1-044 320 2 3 2 1-046 320 4 1-047 320 3 2 3 1-048 320 0 1 0 1-049 320 4 2 2 1-050 320 5 4 3 1-051 320 4 3 4 1-052 320 1 1 0 1-053 320 1 2 0 1-054 320 4 3 3 1-055 320 3 3 3 1-056 320 5 4 4 1-057 320 2 3 3 1-058 320 4 5 4

TABLE 56 Application herbicide No. amount (g/ha) A B C 1-059 320 2 3 2 1-060 320 2 3 2 1-061 320 0 1 1 1-062 320 2 2 2 1-063 320 4 3 2 1-064 320 2 3 2 1-065 320 1 2 2 1-066 320 2 3 2 1-068 320 2 2 2 1-069 320 4 4 4 1-070 320 5 5 5 1-071 320 3 5 4 1-073 320 2 2 1 1-074 320 2 0 0 1-076 320 2 0 4 1-078 320 4 3 3 1-079 320 4 3 4 1-080 320 5 3 4 1-083 320 2 2 2 1-084 320 2 1 0 1-085 320 3 2 2 1-086 320 4 4 4 1-087 320 4 3 1-090 320 2 1 3 1-091 320 5 5 5 1-092 320 4 4 3 1-093 320 3 3 3 1-094 320 4 3 3 1-095 320 4 5 4 1-096 320 4 3 4 1-100 320 4 3 4 1-102 320 1 1 1 1-103 320 4 5 4 1-104 320 4 3 3 1-105 320 3 4 3 1-106 320 5 5 4 1-107 320 5 4 4 1-108 320 4 4 3 1-109 320 0 1 0 1-110 320 4 3 4 1-112 320 1 2 0 1-113 320 2 0 0 1-114 320 0 1 0 1-115 320 3 3 1-116 320 3 4 0 1-118 320 2 3 0 1-119 320 4 1 0

TABLE 57 Application herbicide No. amount (g/ha) A B C 1-120 320 3 3 2 1-121 320 4 4 4 1-122 320 4 3 3 1-123 320 3 2 3 1-124 320 3 3 1 1-125 320 0 2 1 1-126 320 1 3 3 1-128 288 1 3 0 1-129 320 3 4 3 1-131 320 0 1 0 1-132 320 4 4 4 1-133 320 2 2 3 1-134 320 1 3 3 1-135 320 2 2 3 1-136 320 0 2 2 1-137 320 3 3 3 1-138 320 3 3 3 1-139 320 4 3 3 1-144 320 4 4 3 1-145 320 4 4 4 1-146 320 3 3 3 1-147 320 4 2 3 1-148 320 5 5 4 1-149 320 3 3 2 1-150 320 5 5 4 1-151 320 4 4 2 1-152 320 3 3 3 1-153 320 3 3 3 1-154 320 0 2 0 1-155 320 1 2 0 1-156 320 0 3 2 1-157 320 0 1 0 1-158 320 2 3 0 1-159 320 3 1-162 320 3 1 0 1-163 320 4 1-164 320 4 4 4 1-165 320 2 2 1-166 320 2 3 1-168 320 2 2 1-169 320 3 4 4 1-171 320 4 1-172 320 3 4 3 1-173 320 3 2 2 2-001 320 2 2 3 2-002 320 2 1 2 2-003 320 5 3 4

TABLE 58 Application herbicide No. amount (g/ha) A B C 2-005 320 5 3 4 2-006 320 5 5 5 2-007 320 4 4 4 2-008 320 3 2 3 2-009 320 3 2 3 2-010 320 5 4 4 2-011 320 4 3 4 2-012 320 4 5 5 2-013 320 5 3 2 2-014 320 5 5 5 2-015 320 4 5 4 2-016 320 5 5 5 2-017 320 5 4 4 2-019 320 4 3 4 2-020 320 2 2 0 2-021 320 5 4 4 2-022 320 5 5 4 2-023 320 0 1 1 2-024 320 5 4 4 2-025 320 5 4 5 2-026 320 5 5 4 2-027 320 5 4 4 2-028 320 5 4 4 2-029 320 5 4 4 2-030 320 4 3 4 2-031 320 5 4 4 2-032 320 5 5 5 2-033 320 4 3 4 2-034 320 5 4 4 2-035 320 2 2 3 2-037 320 5 5 5 2-038 320 5 4 5 2-039 320 5 5 5 2-040 320 4 3 4 2-041 320 5 4 3 2-042 320 4 3 4 2-043 320 5 4 4 2-044 320 5 4 4 2-045 320 5 3 4 2-047 320 3 5 4 2-048 320 3 4 3 2-049 320 5 5 4 2-050 192 1 0 2 2-051 320 5 5 5 2-052 320 5 4 4 2-053 320 5 4 4 2-054 320 5 4 5

TABLE 59 Application herbicide No. amount (g/ha) A B C 2-056 320 3 3 3 2-057 320 4 4 4 2-058 320 4 4 4 2-059 320 4 3 4 2-060 320 5 3 5 2-061 320 4 5 5 2-062 320 5 4 5 2-060 320 5 4 5 2-061 320 4 5 5 2-062 320 5 4 5 2-063 320 5 4 5 2-064 320 3 4 3 2-065 320 5 4 4 2-066 320 3 3 2-067 320 5 4 5 2-068 320 5 5 4 2-069 320 5 5 5 2-070 320 5 5 5 2-071 320 3 5 5 2-072 320 5 5 5 2-073 320 2 2 3 2-074 320 4 4 3 2-075 320 5 5 5 2-076 320 2 3 2 2-077 320 2 2 2 2-078 320 4 4 3 2-079 320 5 5 5 2-080 320 2 1 0 2-081 320 2 2 2 2-082 320 5 4 3 2-083 320 3 3 3 2-084 320 4 4 3 2-085 320 4 4 3 2-086 320 0 2 1 2-087 320 4 4 3 2-088 141 4 3 4 2-089 320 4 4 5 2-090 320 5 5 4 2-091 320 4 5 4 2-093 320 2 4 3 2-094 320 5 5 4 2-095 320 4 5 5 2-096 320 3 3 3 2-097 320 0 2 2 2-098 320 5 4 3 2-099 320 5 5 4 2-100 320 4 3 4

TABLE 60 Application herbicide No. amount (g/ha) A B C 2-101 320 4 4 5 2-102 320 4 4 4 2-103 320 4 3 4 2-105 320 4 4 4 2-106 320 1 2 3 2-107 320 2 1 2 2-108 320 0 1 2-109 260 1 1 2-110 320 5 5 4 6-002 320 3 2 3 6-004 320 3 0 2 7-002 320 4 2 2

[Nineteenth Table]

TABLE 61 Application herbicide No. amount (g/ha) H D E b 1-001 320 5 5 4 0 1-002 400 4 4 0 1-004 400 4 5 5 0 1-005 400 2 5 5 0 1-008 320 3 0 0 1-010 400 5 5 4 0 1-011 400 5 5 5 0 1-012 400 3 5 0 1-013 320 3 4 3 0 1-014 320 5 2 4 1 1-015 320 5 5 4 1 1-016 320 5 5 5 1 1-017 320 4 3 4 0 1-018 320 4 4 4 2 1-019 320 5 5 5 4 1-020 320 5 4 4 2 1-021 320 5 5 5 3 1-022 320 5 5 4 2 1-024 320 5 4 4 2 1-025 320 4 3 2 2 1-026 320 5 4 4 4 1-027 320 5 5 5 3 1-029 320 4 5 4 4 1-030 320 5 5 5 4 1-031 320 5 4 3 2 1-032 320 5 5 5 2 1-033 320 5 5 5 1 1-034 320 5 5 5 5 1-035 320 5 5 5 4 1-036 320 5 5 5 4 1-037 320 5 5 5 2 1-038 320 5 5 4 2 1-039 320 3 3 3 2 1-040 320 4 5 4 3 1-041 320 4 5 5 2 1-042 320 5 4 1 1-043 320 5 4 5 5 1-044 320 5 4 4 3 1-045 320 1 3 4 0 1-046 320 5 3 3 3 1-047 320 5 5 4 3 1-048 320 5 4 3 0 1-049 320 5 4 4 1 1-050 320 5 5 5 1 1-051 320 4 5 4 0 1-052 320 4 5 5 0 1-053 320 4 4 4 0

TABLE 62 Application herbicide No. amount (g/ha) H D E b 1-054 320 5 5 5 3 1-055 320 5 4 5 2 1-056 320 5 5 5 4 1-057 320 5 5 5 3 1-058 320 5 5 5 4 1-059 320 0 3 3 0 1-060 320 5 4 3 2 1-061 320 5 4 3 1 1-062 320 5 4 4 2 1-063 320 5 5 5 2 1-064 320 5 4 4 2 1-065 320 3 1 3 0 1-066 320 1 4 3 0 1-067 320 5 5 5 2 1-068 320 5 5 5 1 1-069 320 5 5 5 1 1-070 320 4 5 5 0 1-071 320 0 3 5 0 1-072 320 2 1 0 0 1-073 320 5 5 5 4 1-074 320 5 4 3 0 1-075 320 5 4 4 1 1-076 320 5 5 5 3 1-077 320 5 4 3 0 1-078 320 5 5 5 5 1-079 320 5 5 5 5 1-080 320 5 5 5 5 1-081 320 2 0 0 0 1-082 320 4 4 4 0 1-083 320 5 5 5 2 1-084 320 5 5 5 2 1-085 320 5 5 5 3 1-086 320 5 5 5 0 1-087 320 5 5 5 1 1-089 224 3 3 2 0 1-090 320 5 5 5 0 1-091 320 5 5 5 0 1-092 320 5 5 5 4 1-093 320 4 5 4 1 1-094 320 5 4 4 1 1-095 320 4 4 4 1 1-096 320 5 5 4 4 1-100 320 5 5 4 0 1-101 320 1 0 0 0 1-102 320 4 5 4 2 1-103 320 5 5 5 4 1-104 320 5 5 4 0

TABLE 63 Application herbicide No. amount (g/ha) H D E b 1-105 320 5 5 5 0 1-106 320 5 5 5 3 1-107 320 5 5 5 3 1-108 320 5 5 5 1 1-109 320 5 5 3 2 1-110 320 5 5 5 5 1-112 320 3 2 1 0 1-113 320 4 3 3 0 1-114 320 4 4 2 0 1-115 320 5 4 4 0 1-116 320 4 4 0 0 1-117 320 4 4 2 0 1-118 320 5 5 3 3 1-119 320 5 5 2 3 1-120 320 5 5 5 3 1-121 320 5 5 5 3 1-122 320 5 5 5 3 1-123 320 4 4 4 1 1-124 320 4 4 4 0 1-125 320 5 4 3 1 1-126 320 4 4 4 0 1-127 320 4 4 3 0 1-128 288 4 3 3 0 1-129 320 5 5 4 3 1-130 320 5 4 2 2 1-131 320 4 4 3 2 1-132 320 5 5 4 3 1-133 320 4 2 0 0 1-134 320 5 4 2 2 1-135 320 5 4 2 1 1-136 320 4 4 0 2 1-137 320 5 5 4 3 1-138 320 5 5 4 3 1-139 320 4 5 5 1 1-141 320 4 2 3 1 1-142 320 3 1 0 0 1-143 320 4 2 4 0 1-144 320 5 4 2 1-145 320 5 5 5 1-146 320 5 5 4 1-147 320 5 5 3 1-148 320 5 5 5 1-149 320 5 5 5 1-150 320 5 5 5 1-151 320 5 4 4 1-152 320 5 5 4 1-153 320 5 5 3

TABLE 64 Application herbicide No. amount (g/ha) H D E b 1-154 320 3 2 4 1-155 320 1 2 5 1-156 320 3 2 2 1-157 320 4 3 4 1-158 320 5 4 4 1-159 320 5 3 0 1-162 320 4 4 2 1-163 320 5 5 4 1-164 320 5 5 4 1-165 320 5 4 0 1-166 320 4 3 2 1-167 320 1 2 1-168 320 4 3 3 1-169 320 5 4 1 1-170 320 2 4 1 1-171 320 4 4 0 1-172 320 5 5 3 1-173 320 5 4 2 1-174 320 2 2 0 2-001 320 4 4 3 1 2-002 320 5 4 2 2 2-003 200 5 5 5 0 2-005 320 5 5 4 2 2-006 320 5 5 5 5 2-007 320 5 5 5 4 2-008 320 4 5 4 0 2-009 320 5 4 3 4 2-010 320 5 5 5 5 2-011 320 5 5 5 5 2-012 320 4 5 5 2 2-013 320 5 5 5 5 2-014 320 5 5 5 5 2-015 320 5 5 5 4 2-016 320 5 5 5 5 2-017 320 5 5 5 5 2-019 320 5 5 5 5 2-020 320 4 4 4 4 2-021 320 5 5 5 5 2-022 320 5 5 5 5 2-023 320 4 1 0 1 2-024 320 5 5 5 5 2-025 320 5 5 5 5 2-026 320 5 5 5 5 2-027 320 5 5 5 5 2-028 320 5 5 5 5 2-029 320 5 5 5 5 2-030 320 4 5 4 5

TABLE 65 Application herbicide No. amount (g/ha) H D E b 2-031 320 5 5 5 5 2-032 320 5 5 5 5 2-033 320 5 5 5 5 2-034 320 5 5 5 5 2-035 320 5 5 4 5 2-036 320 4 5 4 1 2-037 320 5 5 5 5 2-038 320 5 5 5 5 2-039 320 5 5 4 2-040 320 4 5 4 2-041 320 5 5 5 3 2-042 320 5 5 5 5 2-043 320 5 5 5 5 2-044 320 5 5 5 5 2-045 320 5 5 5 5 2-046 320 2 3 3 0 2-047 320 4 5 5 3 2-048 320 5 5 5 3 2-049 320 5 5 5 1 2-050 192 4 3 3 0 2-051 320 5 5 5 4 2-052 320 5 5 5 5 2-053 320 5 5 5 5 2-054 320 5 5 5 5 2-055 131 2 0 0 0 2-056 320 4 5 4 4 2-057 320 5 5 5 5 2-058 320 5 5 5 5 2-059 320 5 5 5 5 2-060 320 5 5 5 5 2-061 320 5 5 5 5 2-062 320 5 5 5 5 2-063 320 5 5 5 3 2-064 320 1 4 5 0 2-065 320 5 5 5 3 2-066 320 5 5 5 3 2-067 320 5 5 5 5 2-068 320 5 5 5 5 2-069 320 5 5 5 5 2-070 320 5 5 5 3 2-071 320 4 5 5 3 2-072 320 4 5 5 1 2-073 320 4 3 5 2 2-074 320 5 5 4 5 2-075 320 5 5 5 5 2-076 320 5 4 4 1 2-077 320 2 4 3 0

TABLE 66 Application herbicide No. amount (g/ha) H D E b 2-078 320 5 5 3 4 2-079 320 5 5 5 5 2-080 320 4 5 5 3 2-081 320 5 5 5 4 2-082 320 5 5 5 5 2-083 320 4 4 5 0 2-084 320 5 5 5 5 2-085 320 5 5 4 4 2-086 320 5 5 4 3 2-087 320 5 5 5 3 2-088 141 5 5 4 3 2-089 320 4 5 4 2 2-090 320 5 4 5 2-091 320 5 3 4 2-092 320 2 3 2 2-093 320 1 2 5 2-094 320 5 5 5 2-095 320 5 5 5 2-096 320 0 0 5 2-097 320 2 3 4 2-098 320 5 5 5 2-099 320 5 5 4 2-100 320 5 5 3 2-101 320 5 5 4 2-102 320 5 4 1 2-103 320 5 5 1 2-105 320 5 4 5 2-106 320 1 2 0 2-107 320 4 5 4 2-108 320 4 5 4 2-109 260 3 5 2 2-110 320 5 5 3 3-002 320 0 3 0 4-002 320 0 4 0 0 4-003 320 4 3 0 5-001 320 1 0 0 0 6-002 320 5 5 4 0 6-003 320 1 5 0 0 6-004 320 4 5 2 3 7-001 320 1 2 7-002 320 4 4 4 0

[Twentieth Table]

TABLE 67 Application herbicide No. amount (g/ha) F G H I J K L M N O P Q R b c d e f g 1-001 320 4 3 4 1 1 1 1 3 3 5 4 4 4 0 0 3 1 4 4 1-002 320 4 2 5 3 1 2 1 3 3 5 5 4 0 0 3 1 5 4 1-004 320 5 4 5 2 2 2 3 4 4 5 5 1 4 0 4 4 2 4 3 1-005 320 3 3 4 1 0 0 0 4 3 5 1 0 3 0 1 0 0 0 0 1-008 320 3 1 5 0 0 0 0 0 2 3 0 0 0 0 0 0 0 0 0 1-010 320 3 3 4 3 2 1 2 5 5 5 5 1 5 0 1 4 1 5 3 1-011 320 5 4 5 1 1 1 2 5 5 5 5 2 5 0 3 4 0 5 3 1-012 320 3 4 4 0 0 1 1 3 3 5 4 2 4 0 1 2 0 3 4 1-013 320 3 1 4 0 1 1 0 3 3 5 4 1 3 0 0 0 1 3 0 1-014 320 3 3 4 1 1 1 0 4 5 5 5 3 4 1 0 3 1 5 2 1-015 320 4 3 5 3 1 1 3 5 5 5 5 3 5 0 1 4 2 5 4 1-016 320 4 2 5 1 1 1 0 5 5 5 5 2 4 0 0 0 0 5 3 1-017 320 3 0 5 0 0 0 0 5 5 5 4 0 4 0 0 3 0 5 3 1-018 320 0 2 1 0 0 0 0 3 4 5 4 0 4 0 0 0 0 1 0 1-019 320 5 4 5 3 2 2 4 4 5 5 5 4 4 2 2 4 3 5 4 1-020 320 4 3 5 1 1 1 1 2 4 5 4 3 3 0 1 0 1 5 3 1-021 320 4 3 4 1 1 1 1 5 5 5 5 3 4 1 0 3 1 5 3 1-022 320 4 3 5 1 1 1 1 5 5 5 4 2 4 0 2 3 1 4 2 1-024 320 4 3 4 1 0 0 1 4 5 5 4 3 4 0 2 4 0 4 4 1-025 320 3 2 4 0 0 0 0 5 3 5 4 3 3 0 0 3 0 5 2 1-026 320 3 3 3 1 1 1 2 3 4 5 5 2 5 0 0 3 1 5 3 1-027 320 5 4 5 2 2 1 3 5 5 5 5 3 5 0 1 5 2 5 4 1-029 320 5 4 5 1 1 1 1 5 5 5 5 0 5 3 1 3 1 5 1 1-030 320 5 5 5 4 3 3 4 5 5 5 5 4 4 3 2 5 3 5 4 1-031 320 4 4 5 2 1 1 1 5 4 5 4 3 4 0 1 3 1 3 3 1-032 320 5 5 5 2 1 1 2 5 5 5 5 2 4 0 0 4 1 5 4 1-033 320 5 5 5 2 1 1 2 5 5 5 5 3 5 0 2 3 1 5 4 1-034 320 5 5 5 3 1 3 3 5 5 5 5 3 5 5 1 4 2 5 4 1-035 320 5 5 5 2 2 2 3 5 5 5 5 2 5 4 3 4 2 5 3 1-036 320 5 5 5 4 3 3 4 5 5 5 5 4 5 3 3 4 3 5 5 1-037 320 5 4 4 3 2 2 3 5 5 5 4 4 5 0 1 3 3 5 4 1-038 320 5 5 5 3 1 1 2 5 5 5 5 3 5 0 0 4 1 5 4 1-039 320 2 0 4 0 0 0 0 0 1 4 0 0 0 0 0 0 0 2 0 1-040 320 5 4 4 3 3 3 4 5 5 5 5 3 5 0 0 1 3 5 1 1-041 320 5 4 5 3 1 2 4 5 5 5 5 3 4 0 0 2 3 5 0 1-042 320 4 3 5 2 0 0 2 4 4 5 4 3 4 0 1 3 0 5 3 1-043 320 4 3 5 2 1 1 1 5 5 5 4 3 4 4 2 2 0 5 3 1-044 320 4 4 5 1 1 2 4 5 5 5 4 3 5 0 0 3 0 5 4 1-045 320 3 1 2 0 0 0 0 4 4 5 2 2 3 0 0 1 0 3 3 1-046 320 5 5 5 1 0 0 1 5 5 5 4 2 4 1 2 3 0 5 4 1-047 320 4 4 5 1 0 0 1 5 5 5 4 2 4 0 1 3 0 5 4 1-048 320 5 3 5 2 1 1 2 5 4 5 4 3 4 0 0 4 1 5 4 1-049 320 5 4 5 0 2 2 3 5 5 5 4 3 4 0 4 3 1 5 4 1-050 320 5 4 5 3 2 3 3 5 5 5 5 2 5 1 3 4 3 5 5 1-051 320 3 3 4 1 0 1 1 5 3 5 3 2 3 0 0 1 1 3 1 1-052 320 3 1 2 0 1 1 3 4 4 5 2 1 3 0 0 2 0 3 3 1-053 320 3 2 3 1 0 0 0 4 4 5 2 2 4 0 0 3 0 3 1

TABLE 68 Application herbicide No. amount (g/ha) F G H I J K L M N O P Q R b c d e f g 1-054 320 5 4 5 3 3 3 3 5 5 5 4 4 5 0 1 3 3 4 4 1-055 320 4 3 4 1 3 2 3 5 5 5 5 2 4 0 0 3 1 5 4 1-056 320 5 5 5 3 2 2 3 5 5 5 5 4 5 4 4 4 1 5 5 1-057 320 4 4 4 3 2 2 2 5 5 5 5 1 5 0 1 3 0 5 3 1-058 320 5 5 5 3 3 3 2 5 5 5 5 2 5 5 4 4 1 5 4 1-059 320 0 0 2 0 0 0 0 4 2 5 2 0 2 0 0 0 0 0 0 1-060 320 5 3 5 3 2 2 1 4 4 5 4 3 5 3 0 4 3 5 4 1-061 320 3 3 4 3 1 1 1 5 5 5 4 4 5 1 1 4 0 4 4 1-062 320 5 3 5 3 1 0 1 5 4 5 4 4 4 3 0 3 2 4 4 1-063 320 5 5 5 2 2 2 3 4 4 5 4 3 5 0 3 4 2 5 3 1-064 320 5 4 5 1 1 1 1 3 4 3 3 0 0 3 0 4 3 1-065 320 4 1 1 1 0 0 0 3 3 5 4 0 3 0 0 3 0 4 2 1-066 320 3 1 4 1 0 0 0 3 1 5 4 1 4 0 0 3 0 4 0 1-067 320 5 4 5 1 0 0 0 4 1 5 4 3 4 2 0 3 0 4 4 1-068 320 5 4 5 1 1 1 1 3 3 5 4 3 4 2 0 3 1 4 4 1-069 320 5 5 5 2 2 2 4 3 3 5 3 0 1 3 1 5 3 1-070 320 4 4 5 1 0 0 0 4 4 5 5 3 0 0 4 0 4 3 1-071 320 1 0 0 0 0 0 0 3 2 5 1 3 0 0 0 0 2 0 1-072 320 0 0 3 0 0 0 0 1 0 4 2 0 1 0 0 0 0 0 0 1-073 320 5 5 5 3 2 3 3 5 5 5 5 2 5 0 4 3 5 3 1-074 320 4 4 5 1 0 0 0 4 5 4 3 3 0 0 3 0 4 3 1-075 320 3 1 3 0 0 0 0 1 2 5 3 0 3 0 0 0 0 1 1 1-076 320 5 5 5 3 3 3 4 4 4 5 5 2 4 0 3 3 3 5 4 1-077 320 4 2 4 0 0 0 0 2 3 5 4 1 3 0 0 3 0 3 3 1-078 320 5 5 5 4 3 3 4 5 5 5 4 4 4 4 4 5 4 1-079 320 5 5 5 4 2 3 5 5 5 5 4 4 1 5 4 5 5 1-080 320 5 5 5 4 5 4 5 5 5 5 5 4 4 5 5 5 5 1-081 320 0 0 0 0 0 0 0 0 0 4 2 0 0 0 0 0 1 0 1-082 320 4 3 4 0 0 1 1 4 3 5 0 4 0 0 3 0 0 1-083 320 5 5 5 3 0 1 0 5 5 5 4 4 4 1 1 4 1 5 4 1-084 320 5 5 5 3 0 0 0 5 5 5 4 4 5 3 1 4 0 4 4 1-085 320 5 5 5 3 3 3 5 5 5 4 4 5 3 3 4 3 4 4 1-086 320 5 4 5 0 0 0 0 5 4 5 5 1 4 1 1 1 0 5 4 1-087 320 5 5 5 3 3 1 2 5 5 5 4 1 4 0 4 4 2 5 4 1-088 320 0 0 0 0 0 0 0 0 1 2 0 0 0 0 0 0 0 0 0 1-089 224 1 0 3 2 0 0 0 2 1 4 4 0 3 0 0 1 0 3 1 1-090 320 5 3 5 3 1 1 1 3 5 4 1 5 0 1 4 0 5 4 1-091 320 5 5 5 4 2 3 3 5 5 5 5 4 5 0 2 4 3 5 5 1-092 320 5 5 5 2 1 1 1 4 4 5 5 3 5 5 1 4 0 5 3 1-093 320 5 3 5 1 0 1 1 4 4 5 4 1 4 0 4 3 0 5 3 1-094 320 5 4 5 2 1 1 1 4 4 5 5 0 4 0 4 3 1 5 3 1-095 320 5 3 5 1 1 2 1 4 4 5 5 3 5 0 2 3 1 5 3 1-096 320 5 5 5 2 1 2 3 4 5 5 4 4 5 4 4 4 1 5 5 1-100 320 3 1 4 1 0 0 0 3 1 5 3 0 1 0 0 1 0 3 0 1-102 320 3 3 4 0 0 0 0 3 4 5 4 2 4 0 0 1 0 4 2 1-103 320 5 5 5 4 2 3 3 4 5 5 5 4 5 1 2 4 3 5 5 1-104 320 5 5 5 4 1 1 2 4 4 5 5 3 4 0 3 4 2 4 4

TABLE 69 Application herbicide No. amount (g/ha) F G H I J K L M N O P Q R b c d e f g 1-105 320 4 1 4 1 1 1 1 3 3 5 4 1 3 0 1 2 1 4 3 1-106 320 5 5 5 4 1 3 3 4 5 5 5 4 5 3 1 3 3 5 4 1-107 320 5 5 5 4 3 3 3 4 5 5 5 4 5 4 1 5 3 5 5 1-108 320 5 5 5 2 1 2 2 4 5 5 5 3 5 1 1 4 1 5 3 1-109 320 4 3 5 1 0 0 0 4 4 5 4 2 4 0 1 3 0 4 4 1-110 320 5 5 5 4 3 3 3 4 5 5 5 4 5 4 4 4 3 5 5 1-112 320 1 0 2 0 0 0 0 3 4 5 4 0 5 0 0 3 0 5 3 1-113 320 1 0 2 0 0 0 0 1 3 5 4 0 3 0 0 0 0 3 0 1-114 320 1 0 3 0 0 0 0 2 3 5 4 1 3 0 0 0 0 4 0 1-115 320 5 5 5 2 2 1 2 3 4 5 4 3 4 0 0 2 2 5 1 1-116 320 5 4 5 3 1 1 1 4 4 5 5 3 4 0 0 3 2 5 4 1-117 320 1 1 4 0 0 0 0 3 3 5 3 1 3 0 0 3 0 3 1 1-118 320 5 5 5 3 1 1 3 4 4 5 4 4 5 4 0 4 1 5 5 1-119 320 5 4 5 3 3 2 3 5 5 5 4 4 5 3 2 4 3 5 5 1-120 320 5 5 5 3 3 3 5 4 5 5 5 5 5 2 0 4 3 5 5 1-121 320 5 4 5 3 3 3 3 4 5 5 5 3 5 2 2 4 3 5 5 1-122 320 5 5 5 2 3 3 4 5 5 5 5 4 5 2 5 2 5 5 1-123 320 4 3 4 1 0 0 0 4 4 5 4 2 3 0 3 0 4 3 1-124 320 5 3 5 2 0 0 1 5 4 5 3 2 2 1 3 0 3 0 1-125 320 4 1 4 1 0 0 0 3 3 5 4 0 0 2 3 1 5 3 1-126 320 4 3 5 0 0 0 1 3 3 5 5 1 4 1 2 0 5 3 1-127 320 1 1 4 0 0 0 0 2 1 5 3 0 1 0 1 0 2 0 1-128 288 5 2 5 0 1 1 1 3 3 5 5 1 5 0 3 1 5 3 1-129 320 4 4 5 2 1 1 1 3 4 5 5 0 2 4 1 5 3 1-130 320 4 4 5 1 1 1 1 3 3 5 3 4 3 0 3 0 5 4 1-131 320 4 3 4 0 0 0 0 3 3 5 3 0 3 0 3 0 3 0 1-132 320 4 3 5 1 1 1 2 4 3 5 2 4 2 3 1 5 4 1-133 320 3 0 4 0 0 0 0 3 3 4 4 1 2 0 3 0 3 0 1-134 320 4 3 5 0 1 1 1 4 3 5 4 3 4 0 3 1 5 4 1-135 320 4 3 4 1 1 1 1 3 3 5 4 0 1 0 3 0 4 0 1-136 320 4 2 4 0 0 0 1 3 2 5 4 0 3 1 3 0 4 0 1-137 320 4 5 5 3 2 2 4 3 4 5 5 3 5 0 4 2 5 5 1-138 320 4 3 5 2 1 1 3 3 4 5 5 2 5 0 3 1 5 4 1-139 320 5 3 5 1 0 1 0 3 4 5 5 2 5 0 3 1 5 4 1-141 320 3 1 4 0 0 0 0 3 3 4 3 1 3 0 1 0 4 4 1-142 320 1 0 3 0 0 0 0 0 1 4 2 1 0 0 0 0 3 0 1-143 320 2 0 4 0 0 0 0 2 2 4 3 2 3 0 1 0 2 3 1-144 320 3 2 5 2 1 1 0 2 4 5 5 3 4 0 0 4 1 5 4 1-145 320 5 4 5 3 1 2 3 3 4 5 5 1 5 3 0 3 2 5 3 1-146 320 5 5 5 4 2 4 4 4 5 5 5 5 5 5 0 5 3 5 5 1-147 320 4 3 4 3 2 3 3 3 4 5 5 3 5 0 0 3 3 5 5 1-148 320 4 3 5 1 1 3 2 3 5 5 5 4 5 3 0 3 0 5 4 1-149 320 4 3 4 1 1 1 2 3 3 5 5 3 5 1 0 3 0 5 5 1-150 320 4 3 5 3 1 3 3 3 5 5 5 4 5 3 0 4 3 5 5 1-151 320 5 3 5 3 1 3 2 3 5 5 5 4 5 0 0 4 3 5 5 1-152 320 4 3 4 2 0 1 1 3 4 5 4 1 3 0 0 3 0 4 1 1-153 320 4 4 5 3 1 1 2 3 4 5 5 4 4 3 0 5 2 5 3

TABLE 70 Application herbicide No. amount (g/ha) F G H I J K L M N O P Q R b c d e f g 1-154 320 3 2 3 0 0 0 0 2 2 5 4 0 0 0 0 2 0 4 0 1-155 320 3 1 3 0 0 0 0 3 3 5 0 2 0 0 3 0 5 0 1-156 320 2 1 4 1 1 1 2 3 3 5 4 1 3 0 0 3 1 3 0 1-157 320 3 1 3 1 1 1 1 3 3 5 1 2 0 0 3 1 4 2 1-158 320 5 4 5 3 1 2 3 4 4 5 5 3 4 0 0 4 2 5 3 1-159 320 4 4 5 2 1 2 2 3 3 5 5 2 3 0 0 3 1 4 1 1-160 320 1 0 2 0 0 0 0 3 1 4 3 0 1 0 0 2 0 2 0 1-161 320 3 0 3 0 0 0 0 1 0 4 0 0 1 0 0 1 0 1 0 1-162 320 3 1 4 1 1 1 0 3 4 4 3 2 3 0 0 3 0 3 1 1-163 320 4 3 5 2 1 1 1 4 4 5 4 3 2 0 0 4 1 4 3 1-164 320 5 5 5 3 1 1 3 4 5 5 4 4 0 5 3 5 4 1-165 320 3 1 4 0 0 0 2 3 4 5 4 2 4 0 0 1 0 5 4 1-166 320 5 4 5 1 0 1 1 3 4 5 4 1 0 0 4 0 5 4 1-167 320 0 0 2 1 0 1 1 2 2 5 5 2 4 0 0 1 0 5 0 1-168 320 5 4 5 1 0 1 0 3 3 5 5 1 5 3 0 3 1 5 3 1-169 320 4 3 5 1 1 1 1 3 5 5 1 4 0 1 5 1 5 0 1-170 320 4 3 4 1 0 1 1 3 3 5 4 2 4 0 0 2 0 5 3 1-171 320 3 3 5 0 0 0 1 4 4 5 5 2 3 0 0 3 0 5 3 1-172 320 5 4 5 2 1 1 1 5 5 5 5 4 4 3 0 4 1 5 4 1-173 320 4 3 5 2 1 1 1 5 5 5 5 4 4 3 0 4 1 5 4 1-174 320 0 0 0 0 0 0 0 0 4 5 3 3 3 0 0 0 0 4 0 2-001 320 3 0 4 1 0 1 0 5 5 5 5 4 5 0 0 2 0 5 4 2-002 320 4 3 5 3 1 1 1 5 5 5 5 4 5 2 0 3 1 5 4 2-003 320 5 5 5 3 3 3 5 5 5 5 5 4 5 4 1 4 3 5 5 2-005 320 5 4 5 3 3 2 4 5 5 5 5 4 5 0 1 3 3 5 4 2-006 320 5 5 5 3 2 1 4 5 5 5 5 3 5 5 1 4 3 5 4 2-007 320 5 4 5 3 2 2 4 5 5 5 5 1 5 2 0 3 2 5 4 2-008 320 3 2 4 3 1 2 1 5 5 5 5 3 4 1 0 3 2 5 3 2-009 320 4 3 5 3 1 2 1 5 5 5 5 4 4 2 1 4 1 5 4 2-010 320 4 3 5 4 3 3 2 5 5 5 5 4 5 5 3 4 3 5 5 2-011 320 5 3 5 3 3 2 3 5 5 5 5 3 5 5 1 4 1 5 1 2-012 320 4 1 4 3 2 2 2 5 5 5 5 4 4 5 3 4 4 5 4 2-013 320 5 5 5 4 3 3 4 5 5 5 5 4 4 5 3 4 4 5 4 2-014 320 5 5 5 4 4 4 4 5 5 5 5 4 5 5 3 4 4 5 4 2-015 320 5 4 5 2 2 2 2 5 5 5 4 3 3 4 2 2 2 4 3 2-016 320 5 5 5 4 4 4 4 5 5 5 5 3 5 5 1 4 4 5 4 2-017 320 5 5 5 4 3 2 4 5 5 5 5 1 5 5 1 4 3 5 4 2-018 320 2 1 1 0 0 0 0 3 3 3 0 1 2 0 0 0 0 1 0 2-019 320 5 5 5 3 2 2 4 5 5 5 5 3 5 4 0 4 3 5 4 2-020 320 3 3 3 1 0 1 1 5 4 5 4 2 4 2 0 3 1 5 3 2-021 320 5 5 5 3 3 3 4 5 5 5 5 4 5 4 0 4 3 5 4 2-022 320 4 5 5 4 3 3 5 5 5 5 5 4 5 5 1 5 3 5 5 2-023 320 1 1 4 0 0 0 0 3 5 4 3 4 0 0 1 0 4 1 2-024 320 5 5 5 4 3 4 5 5 5 5 5 4 5 5 5 5 4 5 5 2-025 320 5 5 5 4 3 3 4 5 5 5 5 4 5 5 1 4 3 5 4 2-026 320 5 4 5 3 4 3 3 5 5 5 5 4 5 5 2 5 3 5 5 2-027 320 5 5 5 3 4 3 4 5 5 5 5 4 5 4 0 1 3 5 4

TABLE 71 Application herbicide No. amount (g/ha) F G H I J K L M N O P Q R b c d e f g 2-028 320 5 5 5 4 4 4 5 5 5 5 5 4 5 5 3 4 4 5 5 2-029 320 5 5 5 5 5 5 5 5 5 5 5 4 5 5 4 5 5 5 5 2-030 320 5 5 5 4 3 3 5 5 5 5 5 3 5 5 0 4 3 5 5 2-031 320 5 5 5 5 4 5 5 5 5 5 5 5 5 5 5 5 5 5 5 2-032 320 5 5 5 5 3 4 5 5 5 5 5 5 5 5 5 5 5 5 5 2-033 320 5 5 5 5 4 4 5 5 5 5 5 5 5 5 4 5 4 5 5 2-034 320 5 5 5 5 5 5 5 5 5 5 5 5 5 5 3 5 5 5 5 2-035 320 5 5 5 4 3 4 4 5 5 5 5 2 5 5 2 4 4 5 5 2-036 320 5 4 5 1 0 0 3 5 5 5 5 4 4 0 0 2 0 5 3 2-037 320 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 4 5 5 5 2-038 320 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 2-039 320 5 5 5 4 3 3 4 5 5 5 5 4 5 4 3 4 3 5 5 2-040 320 5 3 5 3 1 1 3 5 5 5 5 4 5 4 1 4 2 5 3 2-041 320 4 3 5 3 3 3 4 5 4 5 5 4 4 2 0 4 3 5 4 2-042 320 5 5 5 2 2 1 0 5 5 5 3 1 5 4 0 3 0 4 2 2-043 320 5 4 5 4 3 2 4 5 5 5 5 4 5 3 1 4 3 5 4 2-044 320 5 4 5 2 2 2 3 5 5 5 4 3 5 3 2 4 1 5 3 2-045 320 5 4 5 2 1 1 3 5 5 5 5 3 5 4 3 4 1 5 5 2-046 320 0 1 3 0 0 0 0 4 4 4 2 1 1 0 0 0 0 2 0 2-047 320 5 3 5 3 1 1 3 5 5 5 4 3 5 3 0 3 3 5 3 2-048 320 5 5 5 4 3 4 4 5 5 5 4 4 4 4 5 4 5 5 2-049 320 5 5 5 3 1 3 4 4 3 5 3 4 2 1 4 0 4 3 2-050 192 3 1 3 2 0 0 0 3 2 5 3 0 3 0 0 3 0 3 0 2-051 320 5 5 5 5 4 4 5 5 5 5 5 5 5 4 2 4 4 5 4 2-052 320 5 5 5 5 5 5 5 5 5 5 5 5 4 5 5 5 5 2-053 320 5 5 5 5 5 4 5 5 5 5 5 5 5 4 5 5 5 5 2-054 320 5 5 5 5 4 5 5 5 5 5 5 4 5 5 5 5 5 5 2-055 131 0 0 0 0 0 0 0 4 3 5 4 0 0 0 1 0 1 0 2-056 320 5 3 4 1 1 1 1 4 4 5 5 4 0 1 3 1 5 3 2-057 320 5 5 5 4 4 4 4 5 5 5 5 4 5 4 2 5 4 5 5 2-058 320 5 5 5 5 4 4 4 5 5 5 5 5 5 5 3 5 5 5 5 2-059 320 5 5 5 4 4 4 4 5 5 5 5 5 5 5 3 5 4 5 5 2-060 320 5 5 5 4 3 3 4 5 5 5 5 4 5 5 2 4 4 5 5 2-061 320 5 5 5 4 3 4 3 4 5 5 5 3 5 5 3 4 3 5 4 2-062 320 5 5 5 5 4 5 5 5 5 5 5 5 5 5 5 5 4 5 5 2-063 320 5 5 5 4 3 3 3 5 5 5 5 4 5 4 3 4 3 5 4 2-064 320 3 2 3 0 0 0 0 5 5 5 5 1 5 0 0 3 0 4 3 2-065 320 5 5 5 4 3 3 4 5 5 5 5 3 5 3 4 4 3 5 4 2-066 320 5 5 5 2 3 3 3 4 5 5 5 3 5 4 1 4 3 5 4 2-067 320 5 5 5 5 4 4 3 5 5 5 5 4 5 5 4 5 4 5 5 2-068 320 5 5 5 3 2 2 3 5 5 5 5 4 5 5 3 4 2 5 4 2-069 320 5 5 5 5 3 3 4 5 5 5 5 4 5 5 4 4 3 5 5 2-070 320 5 5 5 5 4 4 4 4 5 5 5 4 5 3 4 3 4 5 5 2-071 320 5 4 5 2 1 1 1 4 5 5 5 3 5 1 2 3 1 5 4 2-072 320 5 5 5 1 1 1 3 5 5 5 5 3 5 1 3 4 1 5 4 2-073 320 1 1 4 1 0 1 0 3 3 5 4 0 2 0 0 2 0 3 0 2-074 320 5 4 5 4 3 3 3 4 5 5 4 3 5 5 3 4 3 5 4

TABLE 72 Application herbicide No. amount (g/ha) F G H I J K L M N O P Q R b c d e f g 2-075 320 5 5 5 5 4 4 4 5 5 5 5 4 5 5 3 5 4 5 5 2-076 320 3 3 5 1 1 1 2 4 5 5 5 3 5 1 0 1 0 5 4 2-077 320 4 2 4 0 0 0 0 4 5 5 4 3 3 0 0 2 0 5 2 2-078 320 5 5 5 3 4 4 5 5 5 5 5 4 5 4 1 4 2 5 5 2-079 320 5 5 5 3 4 2 5 5 5 5 5 4 5 5 2 4 2 5 5 2-080 320 5 3 5 1 1 0 3 5 5 5 4 4 5 3 0 4 0 5 5 2-081 320 4 3 5 3 1 1 1 4 5 5 5 3 4 0 3 2 5 4 2-082 320 5 5 5 2 4 4 4 5 5 5 5 4 4 1 5 4 5 5 2-083 320 5 4 5 2 1 1 1 5 5 5 4 3 4 0 4 0 5 1 2-084 320 5 5 5 4 3 3 4 5 5 5 5 4 3 1 3 3 5 3 2-085 320 5 5 5 4 3 3 4 5 5 5 5 4 4 2 5 3 5 4 2-086 320 5 5 5 3 1 2 4 5 5 5 4 4 5 0 4 2 5 3 2-087 320 5 4 5 4 3 3 4 5 4 5 5 3 0 3 2 5 3 2-088 141 5 5 5 4 3 3 4 5 5 5 5 3 4 0 4 0 5 5 2-089 320 4 4 4 1 2 1 4 4 4 5 5 3 5 0 4 0 5 4 2-090 320 5 4 5 4 3 4 4 3 4 5 4 3 3 1 3 3 5 4 2-091 320 5 5 5 3 2 3 3 4 4 5 5 4 4 2 0 3 3 5 5 2-092 320 0 0 2 1 0 0 0 1 1 3 3 1 1 0 0 1 0 3 0 2-093 320 1 0 1 1 1 1 1 3 2 5 5 2 2 0 0 3 1 2 1 2-094 320 4 4 5 2 1 1 3 5 4 5 5 3 4 3 1 4 1 5 4 2-095 320 5 5 5 4 4 3 5 5 5 5 5 4 4 5 1 5 3 5 5 2-096 320 5 4 5 1 0 0 0 5 5 5 4 3 3 0 0 3 0 5 0 2-097 320 4 3 5 2 1 1 2 3 3 5 4 3 4 0 0 3 0 4 1 2-098 320 5 5 5 4 2 3 4 4 5 5 5 4 4 4 1 4 3 5 4 2-099 320 5 4 5 2 0 1 1 4 4 5 5 4 5 3 0 4 0 5 4 2-100 320 5 4 5 3 2 3 4 5 5 5 5 5 5 5 0 4 0 5 5 2-101 320 5 5 5 3 3 3 4 5 5 5 5 4 5 4 2 5 3 5 5 2-102 320 5 4 5 1 0 1 3 5 5 5 5 3 5 1 0 4 1 5 3 2-103 320 4 3 5 1 0 1 2 4 5 5 5 4 4 2 0 4 0 5 3 2-105 320 5 4 5 4 3 3 4 5 5 5 5 3 5 4 0 4 3 5 5 2-106 320 3 1 3 1 0 0 0 5 4 5 4 3 3 0 0 4 0 5 3 2-107 320 5 3 5 1 0 0 0 5 5 5 5 4 5 3 0 5 0 5 4 2-108 320 4 3 5 1 0 0 0 5 5 5 5 4 5 4 0 4 1 5 5 2-109 256 3 2 4 1 0 1 0 5 5 5 5 3 5 1 0 4 1 5 4 2-110 320 5 4 5 3 2 3 3 5 5 5 5 5 5 4 0 4 3 5 4 3-002 320 0 0 0 0 0 0 0 1 3 4 1 0 0 0 0 0 0 0 0 4-001 320 1 2 3 1 0 0 0 5 5 5 3 3 3 0 0 2 0 2 0 4-002 320 1 1 2 1 0 0 0 5 4 4 3 1 1 0 0 1 0 0 0 4-003 320 2 1 4 0 0 0 1 4 2 5 4 1 2 0 0 4 0 4 1 4-004 320 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0 6-001 320 1 2 1 0 0 0 0 3 3 4 4 2 2 0 0 0 0 3 0 6-002 320 4 3 5 1 0 0 0 5 5 5 5 3 4 0 0 3 0 3 3 6-003 320 4 3 3 0 0 0 0 4 2 3 4 1 1 0 0 0 0 1 0 6-004 320 5 4 5 3 1 2 1 5 5 5 4 4 3 0 0 4 1 2 3 6-005 320 3 1 3 0 1 1 1 4 3 3 1 1 1 0 0 0 0 1 0 6-006 320 0 0 0 0 0 0 0 1 0 3 1 0 1 0 0 0 0 0 0 6-007 320 0 0 0 0 0 0 0 2 3 3 0 0 0 0 0 2 0 3 0

TABLE 73 Application herbicide No. amount (g/ha) F G H I J K L M N O P Q R b c d e f g 6-008 320 0 0 0 0 0 0 0 1 0 3 1 0 0 0 0 1 0 1 0 7-001 320 0 0 1 0 0 0 0 1 0 2 1 0 0 0 0 0 0 0 0 7-002 320 3 2 4 1 0 0 0 3 4 5 4 3 3 0 0 2 0 4 3

INDUSTRIAL APPLICABILITY

The heterocyclic amide compound of the present invention is a novel compound and is useful as selective herbicides for Oryza sative, Zea mays, Glycine max, Triticum aestivum, Beta vulgaris ssp. vulgaris, and Brassica campestris L. 

1. A heterocyclic amide compound of Formula (1):

[where Q is an aromatic heterocycle of any one of Q-1 to Q-5;

W is an aromatic heterocycle of W-1, W-2, or W-3;

X is an oxygen atom or a sulfur atom; R^(1a) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₃₋₆ cycloalkenyl, —C(O)R⁸, —C(O)OR¹⁶, cyano, —OR⁹, —S(O)_(m1)R¹⁰, —N(R¹¹)R¹², C(═NR^(12b))R^(8b), phenyl, phenyl substituted with (R⁷)_(p), naphthyl, or any one group of U-1 to U-25; R^(1b) is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, phenyl, phenyl substituted with (R⁷)_(p), naphthyl, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a)); R^(1c) is C₁₋₆ alkyl; R^(2a) is a halogen atom, C₁₋₆ alkyl, C₁₋₆ haloalkyl, —C(O)R¹⁸, —C(O)OR²⁴, cyano, nitro, —OR¹⁹, —S(O)_(m3)R²⁰, —N(R²¹)R²², phenyl, or phenyl substituted with (R⁷)_(p); when n is an integer of 2 or more, R^(2a) are optionally the same as or different from each other, and when two R^(2a) are adjacent, the two adjacent R^(2a) optionally form a 6-membered ring together with carbon atoms bonded to each R^(2a) by forming —CH═CH—CH═CH—; R^(2c) is C₁₋₆ haloalkyl; R³ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, —C(O)R²⁵, or —C(O)OR²⁶; R^(4a) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R²⁷, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, —NH₂, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, —NHC(O)R⁸, phenyl, phenyl substituted with (R²⁸)_(r), 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a)); R^(4b) is a hydrogen atom, a halogen atom, cyano, nitro, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R²⁷, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, —C(O)OR¹⁶, —OR³⁸, —S(O)_(m3)R²⁰, —NH₂, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, —NHC(O)R⁸, phenyl, phenyl substituted with (R²⁸)_(r), 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a)); R^(4c) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R²⁷, phenyl, phenyl substituted with (R²⁸)_(r), 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a)); R^(4d) is a hydrogen atom, C₁₋₆ alkyl, or (C₁₋₆) alkyl optionally substituted with R³⁵; U-1 to U-6, U-6a, U-7 to U-10, U-10a, U-11, U-11a, U-12, U-12a, U-13, U-13a, U-14 to U-22, U-22a, U-23, U-24, U-25, and U-26 are respective heterocycles of the following structures;

R^(5a) and R^(5b) are each independently a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, phenyl, or phenyl substituted with (R²⁸)_(r); R^(5c) is a hydrogen atom, C₁₋₆ alkyl, or (C₁₋₆) alkyl optionally substituted with R³⁶, or R^(5c) optionally forms a 6-membered ring together with a nitrogen atom to which R^(5c) is bonded and a carbon atom to which R^(4d) is bonded by forming —(CH₂)₄— or —CH═CH—CH═CH— with R^(4d); R⁶ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, —OR¹³, —S(O)_(m2)R¹⁴, phenyl, or phenyl substituted with (R⁷)_(p); R⁷ is a halogen atom, cyano, nitro, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, C₁₋₆ alkylcarbonyl, C₃₋₆ cycloalkylcarbonyl, C₁₋₆ haloalkylcarbonyl, C₃₋₆ halocycloalkylcarbonyl, C₁₋₆ alkoxycarbonyl, C₁₋₆ haloalkoxycarbonyl, C₁₋₆ alkylaminocarbonyl, C₁₋₆ haloalkylaminocarbonyl, di(C₁₋₆ alkylamino)carbonyl, —OR¹⁵, —S(O)_(m3)R²⁰, C₁₋₆ alkylaminosulfonyl, di(C₁₋₆ alkyl)aminosulfonyl, —NH₂, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a)); R⁸ is a hydrogen atom, C₁₋₆ alkyl, or —N(R^(11a))R^(12a); R^(8b) is a hydrogen atom or C₁₋₆ alkyl; R⁹ is a hydrogen atom, C₁₋₆ alkyl, or phenyl; R¹⁰ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, or C₂₋₆ haloalkynyl; R¹¹ and R¹² are each independently a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, phenylsulfonyl, phenyl, phenyl substituted with (R⁷)_(p), U-7, U-8, U-9, or U-14 to U-19, or R¹¹ optionally forms a 3-7-membered ring together with a nitrogen atom to which R¹¹ and R¹² are bonded by forming a C₂₋₆ alkylene chain together with R¹², and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)₂, or N(R³³) and is optionally substituted with an oxo group or a thioxo group; R^(11a) and R^(12a) are each independently a hydrogen atom, C₁₋₆ alkyl, or phenyl, or R^(11a) optionally forms a 3-7-membered ring together with a nitrogen atom to which R^(11a) and R^(12a) are bonded by forming a C₂₋₆ alkylene chain together with R^(12a), and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)₂, or N(R³³) and is optionally substituted with an oxo group or a thioxo group; R^(12b) is —OR^(19b); R¹³ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, —C(O)R⁸, or phenyl; R¹⁴ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, or phenyl; R¹⁵ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, or C₃₋₆ cycloalkenyl; R¹⁶ is a hydrogen atom, C₁₋₆ alkyl, or (C₁₋₆) alkyl optionally substituted with R³⁷; R¹⁸ is a hydrogen atom or C₁₋₆ alkyl; R¹⁹ is a hydrogen atom, C₁₋₆ alkyl, or phenyl; R^(19b) is a hydrogen atom or C₁₋₆ alkyl; R²⁰ is C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, or C₃₋₆ cycloalkenyl; R²¹ and R²² are each independently a hydrogen atom, C₁₋₆ alkyl, or phenyl, or R²¹ optionally forms a 3-7-membered ring together with a nitrogen atom to which R²¹ and R²² are bonded by forming a C₂₋₆ alkylene chain together with R²², and in this case, the alkylene chain optionally contains one O, S, S(O), S(O)₂, or N(R³⁹) and is optionally substituted with an oxo group or a thioxo group; R²⁴ is a hydrogen atom or C₁₋₆ alkyl; R²⁵ and R²⁶ are each independently a hydrogen atom, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, or phenyl; R²⁷ is a halogen atom, cyano, nitro, phenyl, phenyl substituted with (R²⁸)_(r), —C(O)OR¹⁶, —OR²⁹, —S(O)_(m4)R³⁰, 5-6-membered heteroaryl, 5-6-membered heteroaryl (optionally substituted with R²⁸ and R^(28a)), 3-7-membered heterocyclyl, or 3-7-membered heterocyclyl (optionally substituted with R²⁸ and R^(28a)); R²⁸ is a halogen atom, cyano, nitro, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, (C₁₋₆ alkoxy) C₁₋₆ alkyl, —OR³¹, or —S(O)_(m4)R³⁰; when t2, t3, t4, t5, t7, t8, or t9 is an integer of 2 or more, R²⁸ are optionally the same as or different from each other; further when two R²⁸ are adjacent, the two adjacent R²⁸ optionally form a 6-membered ring together with carbon atoms to which each R²⁸ is bonded by forming —CH═CH—CH═CH—; R^(28a) is C₁₋₆ alkyl, C₁₋₆ haloalkyl, (C₁₋₆ alkoxy) C₁₋₆ alkyl, or (C₁₋₆ alkylthio) C₁₋₆ alkyl; R²⁹, R³⁰, and R³¹ are each independently a hydrogen atom, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, or phenyl; R³³ is a hydrogen atom or C₁₋₆ alkyl; R³⁴ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, —OR³³, —S(O)_(m6)R³³, phenyl, phenyl substituted with (R⁷)_(p), U-1, U-3, U-7, U-8, U-9, or U-14 to U-25; R³⁵ is a halogen atom or C₁₋₆ alkoxy; R³⁶ is a halogen atom or C₁₋₆ alkoxy; R³⁷ is C₁₋₆ alkoxy, R³⁸ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, or phenyl; R³⁹ is a hydrogen atom or C₁₋₆ alkyl; t1 is an integer of 0 or 1; m1, m2, m3, m4, m6, and t2 are each independently an integer of 0, 1, or 2; n and t3 are each independently an integer of 0, 1, 2, or 3; p and r are each independently an integer of 1, 2, 3, 4, or 5; t4 is an integer of 0, 1, 2, 3, or 4; t5 is an integer of 0, 1, 2, 3, 4, or 5; t7 is an integer of 0, 1, 2, 3, 4, 5, 6, or 7; t8 is an integer of 0, 1, 2, 3, 4, 5, 6, 7, or 8; and t9 is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9] or a salt thereof.
 2. The heterocyclic amide compound or the salt thereof according to claim 1, wherein W is an aromatic heterocycle of W-1 or W-2; and R^(2a) is a halogen atom, C₁₋₆ alkyl, C₁₋₆ haloalkyl, —C(O)R¹⁸, —C(O)OR²⁴, cyano, nitro, —OR¹⁹, or —S(O)_(m3)R²⁰, and when n is an integer of 2 or more, R^(2a) are optionally the same as or different from each other.
 3. The heterocyclic amide compound or the salt thereof according to claim 2, wherein R^(1b) is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, phenyl, phenyl substituted with (R⁷)_(p), naphthyl, or any one group of U-1 to U-25; R^(4a) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R²⁷, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, —NH₂, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, —NHC(O)R⁸, phenyl, phenyl substituted with (R²⁸)_(r), or any one group of U-1 to U-26; R⁷ is a halogen atom, cyano, nitro, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, C₃₋₆ halocycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkenyl, C₁₋₆ alkylcarbonyl, C₃₋₆ cycloalkylcarbonyl, C₁₋₆ haloalkylcarbonyl, C₃₋₆ halocycloalkylcarbonyl, C₁₋₆ alkoxycarbonyl, C₁₋₆ haloalkoxycarbonyl, C₁₋₆ alkylaminocarbonyl, C₁₋₆ haloalkylaminocarbonyl, di(C₁₋₆ alkyl amino)carbonyl, —OR¹⁵, —S(O)_(m3)R²⁰, C₁₋₆ alkylaminosulfonyl, di(C₁₋₆ alkyl)aminosulfonyl, —NH₂, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, or any one group of U-1 to U-26; and R²⁷ is a halogen atom, cyano, nitro, phenyl, phenyl substituted with (R²⁸)_(r), —C(O)OR¹⁶, —OR²⁹, —S(O)_(m4)R³⁰, or any one group of U-1 to U-26.
 4. The heterocyclic amide compound or the salt thereof according to claim 3, wherein R^(1a) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₃₋₆ cycloalkenyl, —C(O)R⁸, —OR⁹, —S(O)_(m1)R¹⁰, —N(R¹¹)R¹², —C(═NR^(12b))R^(8b), phenyl, phenyl substituted with (R⁷)_(p), U-3, U-5a, U-6a, U-7, U-8, U-10a, U-11a, U-12a, or U-13a; R^(1b) is C₁₋₆ alkyl or (C₁₋₆) alkyl optionally substituted with R⁶; R^(2a) is a halogen atom, C₁₋₆ alkyl, C₁₋₆ haloalkyl, or —S(O)_(m3)R²⁰, and when n is an integer of 2 or more, R^(2a) are optionally the same as or different from each other; R³ is a hydrogen atom or C₁₋₆ alkyl; R^(4a) is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, C₃₋₆ cycloalkyl, phenyl, phenyl substituted with (R²⁸)_(r), or a heterocycle of U-1, U-2, U-7, U-10a, or U-26; R^(4b) is C₁₋₆ alkyl; R^(4c) is a hydrogen atom; R^(4d) is C₁₋₆ alkyl; R^(5a) is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R₂₇, C₂₋₆ alkenyl, or phenyl; R^(5b) is a hydrogen atom or C₁₋₆ alkyl; R^(5c) is C₁₋₆ alkyl, or R^(5c) optionally forms a 6-membered ring together with a nitrogen atom to which R^(5c) is bonded and a carbon atom to which R^(4d) is bonded by forming —(CH₂)₄— or —CH═CH—CH═CH— with R^(4d); R⁷ is a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, or —OR¹⁵; R^(8b) is a hydrogen atom; R⁹ is C₁₋₆ alkyl; R¹⁰ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, or C₂₋₆ alkynyl; R¹¹ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, phenylsulfonyl, phenyl, phenyl substituted with (R⁷)_(p), or U-7; R¹² is a hydrogen atom or C₁₋₆ alkyl; R¹¹ optionally forms a 5-6-membered ring together with a nitrogen atom to which R¹¹ and R¹² are bonded by forming a C₄₋₅ alkylene chain together with R¹², and in this case, the alkylene chain optionally contains one O, S, S(O), or S(O)₂; R^(11a) is C₁₋₆ alkyl; R^(12a) is a hydrogen atom; R¹³ is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, —C(O)R⁸, or phenyl; R¹⁴ is C₁₋₆ alkyl or (C₁₋₆) alkyl optionally substituted with R³⁴; R¹⁵ is C₁₋₆ alkyl; R^(19b) is C₁₋₆ alkyl; R²⁰ is C₁₋₆ alkyl; R²⁷ is a halogen atom, phenyl, phenyl substituted with (R²⁸)_(r), —OR²⁹, —C(O)OR¹⁶, or —S(O)_(m4)R³⁰; R²⁸ is a halogen atom, C₁₋₆ alkyl, or —OR³¹; when t2, t3, t4, t5, or t7 is an integer of 2 or more, R²⁸ are optionally the same as or different from each other; and further when two R²⁸ are adjacent, the two adjacent R²⁸ optionally form a 6-membered ring together with carbon atoms to which each R²⁸ is bonded by forming —CH═CH—CH═CH—; R²⁹ is C₁₋₆ alkyl; R³⁰ is C₁₋₆ alkyl; R³¹ is C₁₋₆ alkyl; R³³ is C₁₋₆ alkyl; and R³⁴ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, —OR³³, —S(O)_(m6)R³³, phenyl, phenyl substituted with (R⁷)_(p), U-1, U-8, or U-22a.
 5. The heterocyclic amide compound or the salt thereof according to claim 4, wherein Q is an aromatic heterocycle of Q-1; and W is an aromatic heterocycle of W-1.
 6. The heterocyclic amide compound or the salt thereof according to claim 5, wherein X is an oxygen atom; R^(1a) a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₃₋₆ cycloalkenyl, —C(O)R⁸, —OR⁹, —S(O)_(m1)R¹⁰, N(R¹¹)R¹², —C(═NR^(12b))R^(8b), phenyl, phenyl substituted with (R⁷)_(p), U-5a, U-6a, U-7, U-8, U-10a, U-11a, U-12a, or U-13a; R^(2a) is a C₁₋₆ alkyl, C₁₋₆ haloalkyl, or —S(O)_(m3)R²⁰, and when n is an integer of 2 or more, R^(2a) are optionally the same as or different from each other; R⁶ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —C(O)R⁸, —C(O)OR¹⁶, —OR¹³, —S(O)_(m2)R¹⁴, or phenyl substituted with (R⁷)_(p); and R²⁷ is a halogen atom, phenyl, —OR²⁹, or —S(O)_(m4)R³⁰.
 7. The heterocyclic amide compound or the salt thereof according to claim 6, wherein R^(4a) is a hydrogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, or C₃₋₆ cycloalkyl; and R²⁷ is a halogen atom or —OR²⁹.
 8. The heterocyclic amide compound or the salt thereof according to claim 4, wherein Q is an aromatic heterocycle of Q-3; and W is an aromatic heterocycle of W-1.
 9. The heterocyclic amide compound or the salt thereof according to claim 8, wherein R^(1a) is a hydrogen atom, a halogen atom, C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R⁶, C₃₋₆ cycloalkyl, (C₃₋₆) cycloalkyl optionally substituted with R⁶, C₂₋₆ alkenyl, C₂₋₆ alkynyl, —C(O)R⁸, —S(O)_(m1)R¹⁰, —N(R¹¹)R¹², phenyl, phenyl substituted with (R⁷)_(p), U-3, U-5a, U-6a, U-8, U-10a, or U-13a; R^(2a) is a halogen atom, C₁₋₆ alkyl, or C₁₋₆ haloalkyl, and when n is an integer of 2 or more, R^(2a) are optionally the same as or different from each other; R⁶ is a halogen atom, —C(O)OR¹⁶, —OR¹³, —S(O)_(m2)R¹⁴, or phenyl substituted with (R⁷)_(p); R⁷ is a halogen atom, C₁₋₆ alkyl, or —OR¹⁵; R⁸ is a hydrogen atom or C₁₋₆ alkyl; R¹¹ is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R³⁴, C₃₋₆ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, phenyl, or phenyl substituted with (R⁷)_(p); R¹¹ optionally forms a 6-membered ring together with a nitrogen atom to which R¹¹ and R¹² are bonded by forming a C₅ alkylene chain together with R¹², and in this case, the alkylene chain optionally contains one O, S, S(O), or S(O)₂; R¹⁶ is a hydrogen atom or C₁₋₆ alkyl; R²⁷ is phenyl substituted with (R²⁸)_(r), —OR²⁹, —C(O)OR¹⁶, or —S(O)_(m4)R³⁰; R²⁸ is a halogen atom or C₁₋₆ alkyl; and R³⁴ is a halogen atom, cyano, C₃₋₆ cycloalkyl, —OR³³, —S(O)_(m6)R³³, phenyl, phenyl substituted with (R⁷)_(p), U-1, or U-8.
 10. The heterocyclic amide compound or the salt thereof according to claim 9, wherein R^(5a) is C₁₋₆ alkyl, (C₁₋₆) alkyl optionally substituted with R²⁷, or C₂₋₆ alkenyl; and R²⁷ is —OR²⁹ or —S(O)_(m4)R³⁰.
 11. An agricultural chemical comprising one or two or more of compounds selected from the heterocyclic amide compound and the salt thereof as claimed in claim 1 as an active component.
 12. A herbicide comprising one or two or more of compounds selected from the heterocyclic amide compound and the salt thereof as claimed in claim 1 as an active component. 